Anionic latex as a carrier for bioactive ingredients and methods for making and using the same

ABSTRACT

This invention relates to latex compositions that incorporate at least one bioactive component such as an antibacterial or an antifungal agent, and methods for making and using such latex compositions. The latex compositions disclosed herein can be prepared by the emulsion polymerization of the latex component monomers in the presence of the at least one bioactive component.

REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Ser. No. 60/839,892, filed onAug. 24, 2006, the contents of which are hereby incorporated byreference.

TECHNICAL FIELD OF THE INVENTION

This invention relates to the field of polymeric materials that can beused in combination with a wide variety of substrates, such as textiles,metal, cellulosic materials, plastics, and the like, and to the field ofbioactive/antimicrobial agents such as antibacterial and antifungalmaterials.

BACKGROUND OF THE INVENTION

The deposition of latex polymer coatings on solid substrates has longbeen utilized to impart certain end-use performance properties to thosesubstrates, such as hydrophobicity, strength, adhesive properties,compatibility, and the like. Depending upon the selection of thestarting monomers, surfactants, emulsion polymerization conditions, andother parameters, the deposited polymers can be designed to carry ananionic, a cationic, or an amphoteric charge, a feature which directlyinfluences coating performance. Further, the resulting latex polymer canbe blended with a range of other functional materials to impartadditional or enhanced features to the final coating material.

In a number of applications, latex polymers can be blended withcompositions containing bioactive compounds that exhibit antimicrobialactivity, in order to provide a latex formulation that can be used inharsh environments where antimicrobial properties are particularlyneeded. These antimicrobial components are usually employed inrelatively small amounts as formulating ingredients that are added afterthe polymer has been made. While such blends are useful, many practicalissues remain in attempts to enhance or control the extent ofantimicrobial protection these compositions might afford. For example,such compositions and methods are often inadequate for providinglong-term protection of substrates or materials in which they aredeployed, especially in their antifungal properties. Methods to augmentor to more finely control the antimicrobial properties are also needed.Regulatory issues associated with introducing a new antimicrobialmaterial, namely the polymer, may be significant. Moreover, approachesto prolong or extend the effectiveness of the antimicrobial propertiesremain elusive.

Therefore, what are needed are new methods and approaches to impart andto enhance antimicrobial activity of latex polymers, as well as thecoatings and articles prepared therefrom. What are also needed aremethods to more closely manage the antimicrobial activity of suchmaterials, including approaches to extend the effectiveness of theirbioactivity.

SUMMARY OF THE INVENTION

This invention encompasses new methods and approaches to incorporatebioactive or antimicrobial ingredients such as antibacterial andantifungal agents into a latex, such that the antimicrobial propertiesof the latex can be enhanced and controlled. The present invention alsorelates to new types of bioactive anionic polymer latex materials. Inone aspect, this disclosure provides a method for incorporatingantimicrobial ingredients into a latex during the emulsionpolymerization process. Previously, antimicrobial agents have been addedto a latex after the polymerization process and in relatively smallamounts as preservatives for the latex product or for the end useapplication such as paints. The present invention allows the use ofhigher concentrations of a wide range of bioactive ingredients,including highly hydrophobic bioactive ingredients, which can be readilyincorporated into the latices such that the resulting latex particlesfunction as carriers for the active ingredients. The thoroughincorporation of an active ingredient in this manner can afford asubstantially homogeneous distribution of the additive and result insuperior and sustained performance compared to pre-made dispersions.

In one aspect of this invention, the emulsion polymerization is carriedout such that the bioactive agents are incorporated into the polymerduring the polymerization, typically by dissolving the bioactivecomponent in a monomer stream. In this manner, the bioactive agents canbe at least partially encapsulated within the latex polymer matrix. Oneadvantage provided by this process is the ability to incorporate orencapsulate large amounts of bioactive ingredients, includinghydrophobic components, without substantially degrading the bioactiveagent. In another aspect, this invention also provides a tunableantimicrobial system based on an anionic latex which function as a typeof carrier for at least one bioactive ingredient, and optionally furtherincluding another bioactive additive that can be blended with thelatices disclosed herein. Thus, these latices can have a multifunctionalpurpose such as providing binding, strength, and dispersion propertiesin addition to being a carrier for an active functional ingredient, andoptionally constituting one component of a blended antimicrobialcomposition.

In one aspect, because the bioactive ingredients are typicallyincorporated into a latex during the emulsion polymerization process,these bioactive components can be at least partially encapsulated withinthe latex polymer matrix. In another aspect, the bioactive componentscan be substantially encapsulated within the latex polymer matrix. Whilenot intending to be bound by theory, it is believed that, by deliveringthe active ingredient to a desired end use application, the latexpolymer with the encapsulated bioactive ingredients can providesustained and controlled exposure of the bioactive ingredients to theenvironment in which they are deployed, thereby providing longer andmore effective protection to the product or the application. Moreover,because the bioactive anionic latices can be formed by existing emulsionpolymerization processes, the polymerization methods advantageouslyallow for the preparation of high molecular weight polymers.

In a further aspect, the methods disclosed herein also provide thepotential to adjust the antimicrobial behavior using a combination ofapproaches to deploy the antimicrobial agent. For example, highlytailored antimicrobial properties can be imparted to a product by bothincorporating the bioactive ingredient into a latex during the emulsionpolymerization process, and by combining the resulting latex productwith the same or at least one different bioactive component in a blend.This approach allows antimicrobial properties to be selected andadjusted using the polymer, the additive, or both, depending on thecircumstances and the performance required.

In yet a further aspect, the techniques disclosed herein can provide theability to encapsulate larger amounts of the active ingredient into alatex composition than are afforded by standard methods. For example,antimicrobial components are usually employed in relatively smallamounts as formulating ingredients once the latex polymer has beenprepared, and such bioactives typically are utilized at concentrationsranging up to about 1000-2000 ppm. In contrast, the antimicrobialcomponent of the latex compositions of this invention can be utilized inconcentrations as high as about 40 weight percent based on the totalmonomer weight. In this aspect, this invention can provide stable,concentrated dispersions that can be used as such, or as an additive, orconcentrated dispersions that can be diluted and added to other systemswhich require antimicrobial protection. High antimicrobial componentconcentrations provide flexibility and ensure the utility of these latexcompositions as concentrates as well as in non-concentrated form.

While the methods disclosed herein can be applied to any bioactive agentthat a particular end use requires, the present disclosure is primarilydrawn to providing or enhancing the antimicrobial properties of a latex,substrate, or particular end product. The relevant antimicrobialactivity can include antibacterial activity, antifungal activity,antiviral activity, antiparasitic activity, or any combination thereof,depending upon the particular selection of bioactive agents. As usedherein, the general term “bioactive” component, agent, or ingredient isused interchangeably with the term “antimicrobial” component, agent, oringredient.

In another aspect, this invention provides a bioactive anionic polymerlatex comprising:

-   -   a) a latex polymer comprising the polymerization product of: i)        at least one ethylenically unsaturated first monomer; and ii)        optionally, at least one ethylenically unsaturated second        monomer that is anionic or a precursor to an anion;    -   b) at least one bioactive component at least partially        encapsulated within the latex polymer; and    -   c) optionally, at least one sterically bulky component        incorporated into the latex polymer.        While the inventive latices of this disclosure are anionic in        nature, it is not necessary that the anionic charge of these        latices be imparted by a monomer that is anionic or a precursor        to an anion, that is, an anionic monomer. For example, an        anionic initiator or an anionic surfactant that can be        polymerizable or non-polymerizable can be used to introduce the        anionic charge to the inventive latices. Accordingly, in this        aspect, the at least one ethylenically unsaturated second        monomer that is anionic or a precursor to an anion is described        as an optional feature of the bioactive anionic polymer latex.

When more than one ethylenically unsaturated first monomer is used toconstitute the first monomer component, each of these first monomers isselected independently. Similarly, when more than one ethylenicallyunsaturated second monomer that is anionic or a precursor to a anion,referred to herein as the “anionic” monomer, is used to constitute thesecond monomer component, each of these second monomers is selectedindependently. A wide range of weight percentages of the at least onefirst monomer and the at least one second monomer can be used in thisinvention. For example, the latex can comprise from about 0.01 percentto 100 percent by weight of the ethylenically unsaturated first monomer,based on the total monomer weight, and the latex can comprise from 0percent to about 99.99 percent by weight of the ethylenicallyunsaturated second monomer that is anionic or a precursor to an anion,based on the total monomer weight.

Further, the latices of this invention can also comprise a stericallybulky component which is incorporated into the anionic polymer latex tosterically stabilize the latex. These sterically bulky components caninclude, but are not limited to, monomers, polymers, and mixturesthereof as set forth below. Thus, a monomer can be incorporated as aco-monomer that can attach to, or constitute a portion of, the backboneof the anionic polymer, examples of which include an alkoxylatedethylenically unsaturated third monomer. A polymer can be incorporatedby adsorbing or being grafted onto the latex surface, an example ofwhich includes polyvinyl alcohol.

While the at least one sterically bulky component incorporated into thelatex polymer is an optional component, this invention also provides foruse of a wide range of amounts and concentrations of this component.Thus, as will be understood by the skilled artisan, in bioactive anionicpolymer latices that do not incorporate at least one sterically bulkycomponent, latex stability can be enhanced by increasing the relativeproportion of the anionic second monomer, by varying the amount and typeof the initiator used, by the addition of surfactants such as nonionicor anionic surfactants, and the like, or any combination of suchmethods. The relative proportion of the anionic second monomer can bereduced and/or surfactants can be eliminated in the presence of at leastone sterically bulky component.

In still another aspect, this invention provides a method of making abioactive anionic polymer latex comprising initiating an emulsionpolymerization of an aqueous composition comprising, at any time duringthe emulsion polymerization:

-   -   a) at least one ethylenically unsaturated first monomer;    -   b) optionally, at least one ethylenically unsaturated second        monomer that is anionic or a precursor to an anion;    -   c) at least one anionic surfactant;    -   d) at least one bioactive component;    -   e) at least one free-radical initiator;    -   f) optionally, at least one sterically bulky ethylenically        unsaturated third monomer;    -   g) optionally, at least one sterically bulky polymer; and    -   h) optionally, at least one nonionic surfactant.        In this aspect, because the anionic latices of this invention        carry a net negative charge, when an anionic latex is prepared        in the absence of the optional second anionic monomer, the        overall negative charge of the latex can be imparted to the        latex by a free radical initiator, by an anionic surfactant, by        an anionic sterically bulky component, or by any combination        thereof.

In one aspect of the invention, the at least one bioactive component canbe dissolved in the monomer feed at any time during the emulsionpolymerization process. Further, in another aspect, the aqueouscomposition components and the at least one bioactive component can beprovided as a dispersion prior to initiating the emulsionpolymerization. Thus, this invention provides for batch processes, inwhich the at least one bioactive component is present in the seed stage.In this aspect, the emulsion polymerization is initiated when all thecomponents of the composition, including the at least one bioactivecomponent, are present from the time of initiation. Further, thisinvention also provides for semi-continuous processes in which theemulsion polymerization is initiated at a time when all components ofthe composition are not present from the time of initiation, but someare added at various times after initiating the polymerization. In thisaspect, for example, the at least one bioactive component can be addedat any time after the seed stage. In another aspect, for example, anyother component or combination of components provided above can be addedat any time after the seed stage, except for at least a portion of thetotal amount of any component that is required to initiate and propagatean emulsion polymerization. Thus, the bioactive anionic latex providedherein can be made by any variety of batch or by a semi-continuousprocesses.

In one aspect, the bioactive latices of this invention can be providedor used as coatings, which can be applicable to medical implants,including artificial ball and socket joints, rods, stents, dentalimplants, pins, screws, catheters, and the like. Such coatings can alsobe provided on everyday surfaces, such as air-conditioning coils, airfilters, pipes, roofing, bathroom items, kitchen items, and the like.Such a coating can prevent microbial infections, such as bacteria andmold, in vehicles as well as homes, hospitals, and other buildings.Further examples of uses of the resultant products are use as an aqueousdispersion or directly in powder form, for example, for sterilizingcooling-water circuits, or indirect use, for example by addition topaints or other surface coatings.

These and other features, aspects, embodiments, and advantages of thepresent invention will become apparent after a review of the followingdetailed description of the invention. It should be understood, however,that these aspects, embodiments, and examples are provided forillustrative purposes only, and are not to be construed in any way asimposing limitations upon the scope thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new latex polymeric materials that can beused in combination with a wide variety of substrates, such as textiles,metal, cellulosic materials, plastics, and the like, in which thepolymeric materials include bioactive components incorporated into thelatex polymer. This invention also provides new methods and processesthat allow incorporating high concentrations of an active ingredientsuch as antifungal agents during the emulsion polymerization. In oneaspect, for example, the disclosed process can be used to incorporatefrom about 0.01% to about 40%, based on the total monomer weight (“phm”or parts per hundred of monomer), of a substantially hydrophobicbioactive ingredient during the emulsion polymerization. While thebioactive ingredient can be introduced at any stage during thepolymerization process including very early during the seed formationstage, in one aspect, the bioactive component or additive (bioadditive)can be added during the later stages of polymerization process, forexample, when from about 30% to about 90% of the monomer has been fedinto the polymerization reactor.

Useful bioactive additives can be solids, liquids, or combinationsthereof. Many of the bioactive additives that can be employed in thisinvention are substantially water insoluble or have limited solubilityin water. In this aspect, the typical water insoluble, hydrophobicbioactive agent can be soluble in at least one of the monomers employedin the emulsion polymerization. Thus, the typical hydrophobic bioactiveingredient can be introduced into the polymerization reactor bysubstantially or partially dissolving it in a monomer feed at theappropriate time. Therefore, the typical ingredients chosen forimparting antimicrobial properties usually will be soluble in themonomers that are used to make the polymer latex. In another aspect,useful bioactive additives in this invention can also be substantiallywater soluble, examples of which include o-phenylphenate (deprotonatedo-phenylphenol), and similar agents. In this aspect, it is not necessarythat such a hydrophilic bioactive additive be soluble in any monomerthat is to be polymerized.

In another aspect, it is not required that antimicrobial ingredients besoluble in at least one of the monomers used, as these ingredients canalso be added as a pre-made dispersion in water. In this aspect, thedispersions can be made, among other ways, by using a relativelyconcentrated amount of the additive and dispersing by using surfactants,dispersants, and the like, and typically employing a mixing device suchas a high speed mixer, a homogenizer, an Eppenbach mixer, or similardevices. In such a case, the dispersion can be fed into the reactor todeliver the appropriate amount of active ingredient into the latex.

In one aspect, this invention encompasses a bioactive anionic polymerlatex comprising:

-   -   a) a latex polymer comprising the polymerization product of: i)        at least one ethylenically unsaturated first monomer; ii)        optionally, at least one ethylenically unsaturated second        monomer that is anionic or a precursor to an anion;    -   b) at least one bioactive component at least partially        encapsulated within the latex polymer; and    -   c) optionally, at least one sterically bulky component        incorporated into the latex polymer.        As provided herein, the at least one sterically bulky component        incorporated into the latex polymer can be selected        independently from at least one sterically bulky ethylenically        unsaturated third monomer, at least one sterically bulky        polymer, or any combination thereof. Each of these components,        as well as optional or additional components, is considered        herein.

In another aspect, this invention also encompasses a method of making abioactive anionic polymer latex comprising initiating an emulsionpolymerization of an aqueous composition comprising, at any time duringthe emulsion polymerization:

-   -   a) at least one ethylenically unsaturated first monomer;    -   b) optionally, at least one ethylenically unsaturated second        monomer that is anionic or a precursor to an anion;    -   c) at least one anionic surfactant;    -   d) at least one bioactive component;    -   e) at least one free-radical initiator;    -   f) optionally, at least one sterically bulky ethylenically        unsaturated third monomer;    -   g) optionally, at least one sterically bulky polymer; and    -   h) optionally, at least one nonionic surfactant.

In yet another aspect, this invention provides a method of making abioactive anionic polymer latex comprising:

-   -   a) providing an aqueous composition comprising:        -   i) at least one ethylenically unsaturated first monomer;        -   ii) optionally, at least one ethylenically unsaturated            second monomer that is anionic or a precursor to an anion;        -   iii) at least one anionic surfactant;        -   iv) optionally, at least one sterically bulky ethylenically            unsaturated third monomer;        -   v) at least one free-radical initiator; and        -   vi) optionally, at least one nonionic surfactant;    -   b) initiating an emulsion polymerization of the composition; and    -   c) adding at least one bioactive component to the composition        during the emulsion polymerization process.

In this aspect, at least one anionic surfactant is typically used toprepare the bioactive anionic polymer latex. The at least one anionicsurfactant that is employed can be in the form of an anionic surfactantthat also does not constitute an ethylenically unsaturated secondmonomer, or the at least one anionic surfactant can be an ethylenicallyunsaturated second monomer that is anionic or a precursor to an anion.In the latter case, the second monomer that is anionic or a precursor toan anion functions both as an ethylenically unsaturated second monomerand as an anionic surfactant. In any event, when an anionic latex isprepared in the absence of the optional second anionic monomer, theoverall negative charge of the latex can be imparted to the latex by afree radical initiator, by an anionic surfactant, by an anionicsterically bulky component, or by any combination thereof.

Many compounds and species that can be used as ethylenically unsaturatedfirst monomers and sterically bulky components are disclosed in theEuropean Patent Number EP 1109845 and the corresponding PCT PublishedPatent Application WO 00/8008077, each disclosure of which isincorporated herein by reference in its entirety.

Ethylenically Unsaturated First Monomers

Various ethylenically unsaturated first monomers can be used in thelatex of the present invention. Examples of suitable first monomers canbe found at least in U.S. Pat. No. 5,830,934, U.S. Patent ApplicationPublication Numbers 2005/0065284 and 2005/0003163, and European PatentNumber EP 1109845, all to Krishnan, each disclosure of which isincorporated herein by reference in its entirety. In this aspect,examples of such monomers include, but are not limited to, vinylaromatic monomers, halogenated or non-halogenated olefin monomers,aliphatic conjugated diene monomers, non-aromatic unsaturated mono- ordicarboxylic ester monomers, unsaturated alkoxylated monoester ordiester monomers, unsaturated diesters of an acid anhydride monomer,nitrogen-containing monomers, nitrile-containing monomers, cyclic oracyclic amine-containing monomers, branched or unbranched alkyl vinylester monomers, aryl vinyl ester monomers, halogenated ornon-halogenated alkyl(meth)acrylate monomers, halogenated ornon-halogenated aryl(meth)acrylate monomers, carboxylic acid vinylesters, acetic acid alkenyl esters, carboxylic acid alkenyl esters, avinyl halide, a vinylidene halide, or any combination thereof, any ofwhich having up to 20 carbon atoms. Thus, the ethylenically unsaturatedfirst monomer is selected from a monomer that is not anionic and is nota precursor to an anion under the reaction and workup procedures. It isthe Applicant's intent to disclose both acrylate and methacrylatemoieties when either moiety is disclosed in a suitable monomer. Thus,the disclosure that an acrylate monomer is a suitable ethylenicallyunsaturated first monomer also encompasses the disclosure that thecorresponding methacrylate monomer is also a suitable first monomer. Theabbreviation (meth)acrylate can be used to represent such a disclosure.

Many different ethylenically unsaturated first monomers can be used inpreparing the bioactive latices of this invention. In one aspect,suitable examples of ethylenically unsaturated first monomers include,but are not limited to, styrene, para-methyl styrene, chloromethylstyrene, vinyl toluene, ethylene, butadiene, methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate,pentyl(meth)acrylate, glycidyl(meth)acrylate, isodecyl(meth)acrylate,lauryl(meth)acrylate, (meth)acrylonitrile, (meth)acrylamide,N-methylol(meth)acrylamide, N-(isobutoxymethyl)(meth)acrylamide, vinylneodecanoate, vinyl versatate, vinyl acetate, C₃-C₈ alkyl vinylethers,C₃-C₈ alkoxy vinyl ethers, vinyl chloride, vinylidene chloride, vinylfluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene,perfluorobutyl ethylene, perfluorinated C₃-C₈ alpha-olefins, fluorinatedC₃-C₈ alkyl vinylethers, perfluorinated C₃-C₈ alkyl vinylethers,perfluorinated C₃-C₈ alkoxy vinyl ethers, and the like, or anycombination thereof. Thus, halogenated analogs of suitable ethylenicallyunsaturated first monomers are encompassed by this disclosure, and it isApplicant's intent to disclose any and all suitable halogen-substitutedanalogs or derivatives of these monomers, including fluorine-substitutedanalogs, chlorine-substituted analogs, bromine-substituted analogs, andiodine-substituted analogs. The term “halogen-substituted” is meant toinclude partially halogen substituted and perhalogen substituted, inwhich any halogen substituents can be the same or can be different. Inthis aspect as well, it is the Applicant's intent to disclose bothacrylate and methacrylate moieties when either moiety is disclosed in asuitable monomer.

In another aspect, the ethylenically unsaturated first monomer can behalogenated or can be non-halogenated. Similarly, the ethylenicallyunsaturated first monomer can be fluorinated or can be non-fluorinated.For example, fluorinated analogs of alkyl acrylates or methacrylates canbe used, as well as the non-fluorinated compounds. The ethylenicallyunsaturated first monomer can also be chlorinated or can benon-chlorinated. The ethylenically unsaturated first monomer can also bebrominated or can be non-brominated. The ethylenically unsaturated firstmonomer can also be iodinated or can be non-iodinated. For example,fluorinated analogs of alkyl acrylates or methacrylates can be used, aswell as the non-fluorinated compounds.

In yet another aspect of this invention, the latices provided herein cancomprise from about 0.01 percent to 100 percent by weight of theethylenically unsaturated first monomer, based on the total monomerweight. In this aspect, the latex of this invention can also comprisefrom about 0.1 percent to about 99.9 percent, from about 1 percent toabout 99 percent, from about 5 percent to about 98 percent, from about10 percent to about 95 percent, from about 25 percent to about 92percent, from about 35 percent to about 90 percent, from about 50percent to about 87 percent, or from about 65 percent to about 85percent by weight of the ethylenically unsaturated first monomer, basedon the total monomer weight. In this aspect, the Applicant's intent isto disclose individually each possible number that such ranges couldreasonably encompass, as well as any sub-ranges and combinations ofsub-ranges encompassed therein. Suitable weight ranges of the at leastone ethylenically unsaturated first monomer are a function of the designproperties and the intended use of the material, as appreciated by theskilled artisan.

Optional Ethylenically Unsaturated Anionic Second Monomers

In still another aspect, the latex polymer of the present invention alsocomprises the polymerization product of at least one ethylenicallyunsaturated second monomer that is anionic or a precursor to an anion.As provided herein, the at least one ethylenically unsaturated secondmonomer can be collectively referred to by the term “anionic monomer,”that is, any monomer which possesses or can be made to posses a negativecharge. In one aspect, this negative charge may be imparted as a resultof hydrolysis and formation of an acidic functionality that is readilydeprotonated, or by way of another reaction known to one of ordinaryskill that can result in a negatively-charged moiety. Such a reaction,for example a hydrolysis reaction, can take place at any stage in theemulsion polymerization process, such as in the component monomer, in anoligomer, in the resulting polymer, or any combination thereof. Inanother aspect, the negative charge may result from a pre-existing acidor salt functionality in the component monomer used to prepare the latexpolymer. The anionic monomer is typically incorporated into the latexpolymer by virtue of its ethylenic unsaturation.

Examples of suitable anionic monomers can be found at least in U.S.Patent Application Publication Numbers 2005/0065284 and 2005/0003163, toKrishnan. In this aspect, examples of suitable anionic monomers include,but are not limited to, a monomer based on the half ester of anunsaturated dicarboxylic acid monomer, an unsaturated mono- ordicarboxylic acid monomer, a sulfate-containing monomer, asulfonate-containing monomer, a phosphate-containing monomer, aphosphonate-containing monomer, an unsaturated anhydride, a monoester ofan acid anhydride, or any combination thereof, any of which having up to20 carbon atoms. When more than one ethylenically unsaturated secondmonomer is used to constitute the anionic monomer component, eachanionic monomer is selected independently.

Further, suitable examples of ethylenically unsaturated anionic monomersthat can be used in the latex of the present invention include, but arenot limited to, (meth)acrylic acid, maleic acid, maleic anhydride,2-sulfoethyl(meth)acrylate, styrene sulfonate,2-acrylamido-2-methylpropane sulfonic acid, monomethyl maleate, itaconicacid, itaconic anhydride, fumaric acid, or any combination thereof.

As described for the first monomers, halogenated analogs of suitableethylenically unsaturated second monomers are also encompassed by thisdisclosure, and it is Applicant's intent to disclose any and allsuitable halogen-substituted analogs or derivatives of these monomers,including fluorine-substituted analogs, chlorine-substituted analogs,bromine-substituted analogs, and iodine-substituted analogs. The term“halogen-substituted” is meant to include partially halogen substitutedand perhalogen substituted, in which any halogen substituents can be thesame or can be different. In this aspect as well, it is the Applicant'sintent to disclose both acrylate and methacrylate moieties when eithermoiety is disclosed in a suitable monomer.

In a further aspect, the latex polymer of this invention can comprisefrom 0 to about 99.99 percent by weight of the ethylenically unsaturatedsecond monomer that is anionic or a precursor to an anion, based on thetotal monomer weight. In this aspect, the latex of this invention canalso comprise from about 0.01 to about 99 percent, from about 0.1 toabout 98 percent, from about 0.5 to about 95 percent, from about 1 toabout 90 percent, from about 2 to about 80 percent, from about 3 toabout 70 percent, from about 4 to about 60 percent, from about 5 toabout 50 percent, from about 7 to about 40 percent, from about 10 toabout 30 percent, or from about 15 to about 25 percent, by weight of theanionic second monomer, based on the total monomer weight. In thisaspect, the Applicant's intent is to disclose individually each possiblenumber that such ranges could reasonably encompass, as well as anysub-ranges and combinations of sub-ranges encompassed therein.

Sterically Bulky Components

As disclosed herein, one aspect of this invention encompasses an anionicpolymer latex comprising: a) a latex polymer as disclosed herein; b) atleast one bioactive component at least partially encapsulated within thelatex polymer; and c) optionally, at least one sterically bulkycomponent incorporated into the latex polymer. The at least onesterically bulky component incorporated into the latex polymer can beselected independently from at least one sterically bulky ethylenicallyunsaturated third monomer, at least one sterically bulky polymer, or anycombination thereof. In this aspect, and while not intending to be boundby theory, this sterically bulky component is typically incorporatedinto the anionic polymer latex to sterically stabilize the latex.

As used herein, the term “incorporated” with respect to the use of theat least one sterically bulky ethylenically unsaturated third monomerincludes, but is not limited to, the attachment of this third monomer tothe anionic polymer, for example, by co-polymerization of the thirdmonomer with the first monomer and the optional second monomer disclosedherein, to form the anionic polymer latex. Further, the term“incorporated” with respect to the at least one sterically bulkyethylenically unsaturated third monomer can also include the attachmentof this third monomer to the anionic polymer in any other fashion, suchas, for example, by grafting onto the polymer backbone. In anotheraspect, the term “incorporated” with respect to the use of the at leastone sterically bulky polymer includes, but is not limited to, theattachment or association of this polymer into the latex for methodsincluding, but not limited to, adsorbing or grafting the stericallybulky polymer onto the latex surface. For example, polyvinyl alcohol canbe incorporated into the latex in this manner. This stericallystabilizing component can encompass a nonionic monomer or nonionicpolymer which incorporate steric stabilization to the latex particlewithout affecting the deposition characteristics of the anionic polymerlatex.

Exemplary monomers that can be used as sterically bulky ethylenicallyunsaturated third monomers include, but are not limited to, thoseethylenically unsaturated monomers that contain alkoxylated (forexample, ethoxylated or propoxylated) functionalities. In one aspect,examples of such monomers include, but are not limited to, at least onea sterically bulky ethylenically unsaturated compound selectedindependently from the following:

a) CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), wherein R^(1A), R^(2A), andR^(3A) can be selected independently from H or an alkyl group havingfrom 1 to 6 carbon atoms, inclusive, and m can be an integer from 1 to30, inclusive. In this aspect, R^(1A), R^(2A), and R^(3A) can also beselected independently from H or methyl, m can be an integer from 1 to10, inclusive;

b) CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B), whereinR^(1B), R^(2B), and R^(3B) can be selected independently from H or analkyl group having from 1 to 6 carbon atoms, inclusive, and n and p canbe integers selected independently from 1 to 15, inclusive. Also in thisaspect, R^(1B), R^(2B), and R^(3B) can be selected independently from Hor methyl, and n and p can be integers selected independently from 1 to10, inclusive;

c) CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), whereinR^(1C), R^(2C), and R^(3C) can be selected independently from H or analkyl group having from 1 to 6 carbon atoms, inclusive, and q and r canbe integers selected independently from 1 to 15, inclusive. Further tothis aspect, R^(1C), R^(2C), and R^(3C) can be selected independentlyfrom H or methyl, and q and r can be integers selected independentlyfrom 1 to 10, inclusive; or

d) any combination of any of these compounds.

In another aspect of this invention, a number of other types ofunsaturated compounds can be used as sterically bulky ethylenicallyunsaturated third monomers include, but are not limited to,polymerizable surfactants. Thus, further examples of suitable stericallybulky ethylenically unsaturated third monomers include, but are notlimited to, alkoxylated monoesters of a dicarboxylic acid; alkoxylateddiesters of a dicarboxylic acid; alkyl allyl sulfosuccinate salts; vinylsulfonate salts; polyoxyethylene alkylphenyl ethers such as NOIGEN RN™;polyoxyethylene alkylphenyl ethers ammonium sulfate such as HITENOL BC™;or any combination thereof. In this aspect, for example, ethoxylatedmono- and diesters of diacids such as maleic and itaconic acids can alsobe used to achieve the desired stabilizing effect. Acrylate,methacrylate, vinyl and allyl analogs of surfactants, referred to aspolymerizable surfactants, can also be used in this manner. Examples ofsuch polymerizable surfactants include, but are not limited to, TREMLF-40™ sold by Cognis. In one aspect, these surfactants are typical inthat they possess ethylenic unsaturation that allows the surfactants tobe incorporated into the latex polymer itself, as well as possessinghydrophobic and hydrophilic functionality that varies. In anotheraspect, surfactants that are particularly applicable to the presentinvention include the nonionic surfactants, wherein the hydrophiliccharacter is believed to be attributable to the presence of alkyleneoxide groups. Examples of suitable nonionic surfactants include, but arenot limited to, ethylene oxide, propylene oxide, butylene oxide, and thelike. In such species, the degree of hydrophilicity can vary based onthe selection of functionality.

The at least one sterically bulky component incorporated into the latexpolymer can also constitute at least one polymer. Again, while notintending to be bound by theory, it is thought that such polymersprovide steric stability to the resulting latex polymer. Such polymersare sometimes referred to in the art as protective colloids. Examples ofsterically bulky polymers include, but are not limited to, polyvinylalcohols, polyvinyl pyrollidone, hydroxyethyl cellulose, and the like,including any combination of these materials. Moreover, mixtures orcombinations of any of the aforementioned sterically bulky monomers andany of these sterically bulky polymers can also be used as the at leastone sterically bulky component that is incorporated into the latexpolymer. A number of other monomers and polymers that can be used in thepresent invention that can impart stability are provided in U.S. Pat.No. 5,830,934 to Krishnan et al., the entirety of which is incorporatedherein by reference.

The optional at least one sterically bulky component can be present inan amount ranging from 0 to about 25 percent by weight, based on thetotal weight of the monomers. In this aspect, the latex of thisinvention can also comprise from about 0.1 to about 20 percent, fromabout 0.2 to about 18 percent, from about 0.5 to about 15 percent, fromabout 0.7 to about 12 percent, or from about 1 to about 10 percent byweight of the sterically bulky component, based on the total monomerweight. In this aspect, Applicants' intent is to disclose individuallyeach possible number that such a range could reasonably encompass, aswell as any sub-ranges and combinations of sub-ranges encompassedtherein.

Free Radical Initiators

In still a further aspect, the latex of the present invention caninclude a free radical initiator that can initiate the emulsionpolymerization, the selection of which is known to one of ordinary skillin the art. Because the anionic latices of this invention carry a netanionic charge, when an anionic latex is prepared in the absence of theoptional second anionic monomer, the overall negative charge of thelatex can be supplied by the free radical initiator. Thus, in additionto an anionic monomer, the overall negative charge can be imparted tothe latex by a free radical initiator, by an anionic surfactant, by ananionic sterically bulky component, or by any combination thereof. Thus,while any anionic or nonionic free radical polymerization initiator canbe used, and even low levels of a cationic initiator can be tolerated,typical free radical initiators include, but are not limited to, anionicinitiators including, but not limited to persulfates, peroxides,azo-based compounds, or any combination thereof, that are capable ofimparting an anionic charge to the resulting latex. In this aspect, anyfree radical initiator which generates an anionic species upondecomposition and contributes to the anionic charge of the latex canalso be utilized. Examples of such an initiator include, but are notlimited to, 4,4′-azobis(4-cyano pentanoic acid), which is soldcommercially as WAKO V-501™ by Wako Chemicals of Richmond, Va.

Bioactive/Antimicrobial Agents and their Incorporation

The anionic latex polymerization and encapsulation method disclosedherein can be utilized with a range of antimicrobial agents. Anioniclatex polymers can also be blended with compositions containingbioactive compounds that exhibit antimicrobial activity, in order toprovide a latex formulation that can be used in harsh environments whereantimicrobial properties are particularly needed. In this manner, theantimicrobial properties imparted to an anionic latex by theencapsulation method disclosed herein can be supplemented with at leastone antimicrobial agent in a composition that is blended with theanionic latex polymer.

In this aspect, this invention also provides methods to prepare anantifungal and antibacterial fortified anionic latex and to deposit sucha latex through a wet end process onto pulp fibers, such that theresultant sheet of paper is substantially antifungal and antimicrobial.For example, in one aspect, this invention affords a method fordeposition of the antimicrobial anionic latex onto pulp fibers, eventhough such a method is not facilitated by coulombic forces arising fromopposite charges on the latex and the fibers. Thus, deposition can becarried out with an anionic latex which, although lacking inherentantimicrobial properties, will still function as a carrier for theincorporated bioactive ingredient. Such a deposition typically involvesflocculation of the anionic latex using a cationic ingredient, whichresults in coagulation of the polymer onto the fiber, and provides aslurry of all the components that exhibits varying degrees ofheterogeneity. In this aspect, the typical initiators also includeazo-based compounds and compositions.

As provided herein, a wide range of polymerization conditions can beused. In one aspect, the bioactive component or additive is typicallysoluble in at least one of the monomers employed, and/or soluble in amonomer mixture or composition used. In another aspect, the bioactiveadditive can be introduced at any stage during the polymerizationprocess including very early during the seed formation stage, includinginitiating the emulsion polymerization when all the components of thecomposition, including the at least one bioactive component, are presentat the time of initiation. In another aspect, the bioadditive can beadded during a later stage of polymerization process. For example, thebioactive ingredient can be introduced into the monomer feed when about30 percent of the monomer has been fed into the polymerization reactor.

While not intending to be bound by theory, it is believed thatintroducing the bioactive component into the monomer feed relativelylate in the polymerization process could help minimize degradation ofthe bioactive agent arising from the polymerization conditions. Forexample, it is possible that the bioactive agent could be degraded atthe temperature under which polymerization is conducted, or could reactwith certain monomers or other components. Accordingly, to minimize anysuch degradation process, the bioactive agent can be added at such atime in the process, for example, when the process is more than about50%, more than about 60%, more than about 70%, more than about 80%, ormore than about 90% complete, thus minimizing the contact time betweenthe bioactive agent and other components under the polymerizationconditions. Another approach to minimize degradation of the bioactiveagent is to employ bioactive agents that comprise “latent” bioactivemoieties that can be activated by thermal, chemical, photochemical, orsimilar means, at a suitable time after the emulsion polymerization.

In another aspect of this invention, the bioactive additive can beintroduced at any stage during an emulsion polymerization process,including, for example at such a time during the process at which theresulting antimicrobial latex exhibits a bioactivity that is notsubstantially diminished relative to a standard bioactivity exhibited bythe same antimicrobial latex prepared by adding the bioactive componentwhen the emulsion polymerization is about 50% complete. Thus, thisstandard bioactivity is the activity of the same antimicrobial latexsynthesized from the same bioactive component and the same latex atsubstantially the same concentrations, prepared by adding the bioactivecomponent when the emulsion polymerization is about 50% complete, asevaluated under similar conditions. The term “not substantiallydiminished” is used to refer to any difference in activity of theresulting bioactive latex, relative to this standard bioactivity, thatmeets any one, or more than one, of the following criteria: 1) themeasured activity of the resulting bioactive latex is less than or equalto about 15% lower than the measured activity of the standard; 2) theactivity of the resulting bioactive latex has a numerical activityrating based on an arbitrary activity scale that is less than or equalto about 35% lower than the numerical activity rating of the standard;or 3) the empirically-based descriptive rating of the activity level ofthe resulting bioactive latex is no more than two descriptive ratinglevels lower than the activity rating level of the standard. Themeasurement of antimicrobial activity can be determined according to anyone, or more than one, of the following test standards: ASTM E2180-01;ASTM E2149-01; ASTM E1882-05; ASTM D3273; AATCC Test Method 30, Part 3;AATCC Test Method 100; ASTM D5590. An example of criterion 1) of “notsubstantially diminished” is as follows. A bioactive additive can beintroduced at a time, or introduction can be initiated at a time, duringan emulsion polymerization process so as to provide a resultingantimicrobial latex having a minimum inhibitory concentration (MIC) of0.009 mg/mL, which is less than 15% lower than a MIC of 0.010 mg/mL forthe standard. An example of criterion 2) of “not substantiallydiminished” is as follows. The bioactive additive can be introduced at atime, or introduction can be initiated at a time, during an emulsionpolymerization process so as to provide a resulting antimicrobial latexhaving numerical activity rating of bioactivity based on an arbitraryactivity scale of 5, which is less than 35% lower than the numericalactivity rating of bioactivity of 7 for the standard. An example ofcriterion 3) of “not substantially diminished” is as follows. In anempirically-based descriptive rating system that includes contiguousrating levels of “excellent activity,” “very good activity,” and “goodactivity,” the bioactive additive can be introduced at a time, orintroduction can be initiated at a time, during an emulsionpolymerization process so as to provide a resulting antimicrobial latexhaving an activity rating of “good activity,” as compared to an activityrating of “excellent activity” for the standard. In any of thesemeasurements of activity, the bioactive additive can be introduced atany time during the polymerization process that provides this result, orintroduction can be initiated at a time during the polymerizationprocess that provides the result disclosed above.

In another aspect, it is not necessary to introduce the bioactivecomponent into the monomer feed relatively late in the polymerizationprocess. For example, the bioadditive agent can also be added when about0 percent, about 10 percent, about 20 percent, about 30 percent, about40 percent, about 50 percent, about 60 percent, about 70 percent, about80 percent, about 90 percent, or about 100 percent of the monomer hasbeen fed into the polymerization reactor. In this aspect, the emulsionpolymerization is initiated at a time when all components of thecomposition are not present from the time of initiation, but some areadded at various times after initiating the polymerization, including,but not limited to, the at least one bioactive component. Also in thisaspect, the Applicant's intent is to disclose any and all ranges betweensuch numbers, and to claim individually each possible number that suchranges could reasonably encompass, as well as any sub-ranges andcombinations of sub-ranges encompassed therein.

In another aspect, polymerization can be effected at a range oftemperatures, typically selected between the lowest temperature thataffords reasonable polymerization rates, and the highest temperatureallowable that does not result in substantial degradation ordecomposition of the antimicrobial bioactive ingredient. In one aspect,the polymerization can be carried out at the lowest temperature possiblesuch that polymerization proceeds. In this case, the polymerizationtemperature should be sufficiently low to not substantially degrade ordecompose any bioactive ingredient that is incorporated, yet high enoughsuch that polymerization rates and times are adequate for usefulproduction of the final latex polymer.

The antimicrobial agent can also be fed as a pre-emulsion made byemulsifying a mixture of monomer, additive, surfactants, water, and thelike, using methods and materials known to one of ordinary skill in theart. For example, In this aspect, the dispersions can be made, amongother ways, by using a relatively concentrated amount of the additiveand dispersing by using surfactants, dispersants, and the like, andtypically employing a mixing device such as a high speed mixer, ahomogenizer, an Eppenbach mixer, or similar devices. Moreover, any otherconceivable process or process known to one of ordinary skill thatprovides emulsion polymers in which the additive is a dispersion, anemulsion, a suspension, or the like, or substantially dissolved in themonomer mixture prior to polymerization, can be utilized.

In one aspect, useful antimicrobial agents that provide antifungal andantibacterial properties can be, in many cases, susceptible to oxidationor reduction, especially when exposed to higher temperatures. Thereforein addition to antimicrobial agent solubility, another aspect ofselecting and incorporating antimicrobial agents is diminishing anyoxidation or reduction reaction that would degrade such components. Theprocesses of this invention can typically achieve this result bycontrolling the polymerization temperature, adjusting the time periodthat the active ingredient is added into the reaction to controlexposure to the polymerization temperature, by adding an appropriateoxidant or reductant at some time during the polymerization to diminishor moderate any redox degradation, or any combination of these methods.

In a further aspect of the present invention, the at least one bioactivecomponent can be selected independently from undecylenic acid;undecylenic alcohol; the reaction product of undecylenic acid withhydroxylethyl(meth)acrylate or polyethylene glycol(meth)acrylate; thereaction product of undecylenic alcohol with (meth)acrylic acid, maleicanhydride, or itaconic acid; or any combination thereof. Additionalantimicrobial components that can be used in the present invention areprovided in U.S. Patent Application Publication Number 2005/0003163, toKrishnan, which is incorporated herein by reference in its entirety.Another aspect of this invention provides that the at least onebioactive component can be selected independently from copper, coppersalts, silver, silver salts, zinc, zinc salts, silver oxide, zinc oxide,chlorhexidine, chlorhexidine gluconate, glutaral, halazone,hexachlorophene, nitrofurazone, nitromersol, povidone-iodine,thimerosol, C₁- to C₅-parabens, hypochlorite salts, clofucarban,clorophene, poloxamer-iodine, phenolics, mafenide acetate, aminacrinehydrochloride, quaternary ammonium salts, oxychlorosene, metabromsalan,merbromin, dibromsalan, glyceryl laurate, pyrithione salts, sodiumpyrithione, zinc pyrithione, (dodecyl)(diethylenediamine)glycine,(dodecyl)(aminopropyl)glycine, phenol, m-cresol, n-cresol, p-cresol,o-phenyl-phenol, resorcinol, vinyl phenol, polymeric guanidines,polymyxins, bacitracin, circulin, octapeptins, lysozmye, lysostaphin,cellulytic enzymes, vancomycin, ristocetin, actinoidins, avoparcins,tyrocidin A, gramicidin S, polyoxin D, tunicamycin, neomycin,streptomycin, or any combination thereof.

Yet another aspect of this invention provides that the at least onebioactive component can exhibit fungicidal activity. In this aspect,suitable fungicides that are applicable to this disclosure include, butare not limited to, azoles, quaternary ammonium compounds,dithiocarbamates, dicarboximides, or any combination thereof. Forexample, in this aspect, an azole fungicide can be selected fromazaconazole, biternatol, bromuconazole, cyproconazole, diniconazole,fenbuconazole, flusilazole, flutnafol, imazalil, imibenconazole,metconazole, paclobutrazol, perfuazoate, penconazole, simeconazole,triadimefon, triadimenol, uniconazole, or any combination thereof. Alsoin this aspect, a dithiocarbamate fungicide can be selected frommancozeb, maneb, metiram, zineb, or any combination thereof.

In another aspect, suitable fungicides can include, but are not limitedto, fludioxonil, fluquinconazole, difenoconazole,4,5-dimethyl-N-(2-propenyl)-2-(trimethylsilyl)-3-thiophenecarboxamide(sylthiopham),hexaconazole, etaconazole, triticonazole, flutriafol, epoxiconazole,bromuconazote, tetraconazole, myclobutanil, bitertanol, pyremethanil,cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl, azoxystrobin,ZEN90160™, fenpiclonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl,orfurace, oxadixyl, carboxin, prochloraz, triflumizole, pyrifenox,acibenzolar-S-methyl, chlorothalonil, cymoxanil, dimethomorph,famoxadone, quinoxyfen, fenpropidine, spiroxamine, triazoxide,BAS50001F™, hymexazole, pencycuron, fenamidone, guazatine, and the like,including any combination thereof. Still another aspect of thisinvention provides that suitable fungicides can include, but are notlimited to, benomyl (also known as benlate), captan, carbendazim,capropamid, ethirimol, flutolanil, fosetyl-aluminum, fuberidazole,hymexanol, kasugamycin, iminoctadine-triacetate, ipconazole, iprodione,mepronil, metalaxyl-M (mefenoxam), nuarimol, oxine-copper, oxolinicacid, perfurazoate, propamocarb hydrochloride, pyroquilon, quintozene(also known as PCNB), silthiopham, MON™ 65500, tecnazene, thiabendazole,thifluzamide, thiophenate-methyl, thiram, tolclofos-methyl,triflumizole, and the like, including any combination thereof. Moreoverany combination or mixture of any of these fungicides can be employed.

In yet another aspect of this invention, typical amounts of bioactivecomponent that can be added during the emulsion polymerization can rangefrom about 0.01 percent to about 40 percent by weight bioactiveadditive, based on the total monomer weight. In another aspect, typicalamounts of bioactive component that can be added during the emulsionpolymerization can range from about 0.025 percent to about 35 percent,from about 0.05 percent to about 30 percent, from about 0.1 percent toabout 25 percent, from about 0.25 percent to about 20 percent, or fromabout 0.5 percent to about 15 percent by weight bioactive additive,based on the total monomer weight. In this aspect, the Applicant'sintent is to disclose individually each possible number that such rangescould reasonably encompass, as well as any sub-ranges and combinationsof sub-ranges encompassed therein. As compared to the amount ofantimicrobial component added as a “post-add,” these concentrations ofbioactive additive are typically much larger than the post-add amounts.Among other things, this features provides stable, concentrateddispersions that can be used as concentrates, as additives, or asconcentrated dispersions that can be diluted and added to other systemswhich require antimicrobial protection.

As disclosed herein, in one aspect, the bioactive component is typicallydissolved in the monomer feed during the emulsion polymerizationprocess. Thus, the bioactive additive is typically at least partiallysoluble in one or more of the monomers employed. Further, the bioactiveadditive can be moderately soluble, substantially soluble, or highlysoluble in one or more of the monomers employed. This feature can allow,among other things, the incorporation of hydrophobic bioactiveingredients, the use of high amounts and concentrations of bioactiveingredients, greater control over the antimicrobial properties includingenhancing the effectiveness of the antimicrobial properties, the use ofminimal amounts of surfactant, and at least partial encapsulation of thebioactive ingredient. In some instances, the latex polymer cansubstantially encapsulate the added bioactive component, thus the latexpolymer can function as a type of carrier for the active ingredients.This process also allows for the incorporation of the antimicrobialingredients without substantially degrading the activity of thesecompounds.

In another aspect, useful bioactive additives in this invention can alsobe water soluble to any extent, including substantially water soluble,examples of which include o-phenylphenate (deprotonated o-phenylphenol),and similar agents. Thus, it is not necessary that such a hydrophilicbioactive additive be soluble in any monomer that is to be polymerized.In still another aspect, useful bioactive additives in this inventioncan be substantially insoluble in the monomers being polymerized andsubstantially insoluble in water. In this aspect, a dispersion of thebioactive component can be made by, among other ways, by dispersing acertain concentration of the additive with the use of surfactants andthe like, typically with the use of high speed mixers or homogenizers.

Because the post-added additives are typically dispersions that arepost-mixed into a formulation, it can be difficult to adequatelydisperse the bioactive additive into the polymer film, binder, coating,or the like, in which they are used. Moreover, typical additivedispersions that are used today can cause or be associated with moisturesensitivity and leaching of the additive, and many post-adds do notpersist within the product for a sufficient period of time to provideadequate antifungal protection. The approach provided in this disclosureallows the use of minimal surfactants to incorporate the bioactiveadditives into the latex, and because the bioactives are introducedduring the polymerization, they are typically encapsulated and are noteasily released from the resulting latex. As a result, there can be lessleaching of the bioactive component, and better overall distribution ofthe bioactive ingredient throughout the polymer film, binder, coating,and the like. Accordingly, this method can provide a potentially saferand more environmentally friendly dispersion, while also offeringsustained antifungal or antibacterial protection.

The process disclosed herein also allows the latex to be used as aconcentrate, in contrast to the typical concentrate dispersions that arenot as stable as those provided herein. As a result, the typicalconcentrate dispersions are not as easily manipulated and thereforecannot be incorporated as easily into a finished product, and can havedeleterious effects on performance, such as water sensitivity, if dosageis increased. A concentrate of the latex provided herein can be dilutedand used with or without other materials if such materials are needed toprovide an adequate level of additive. Intimate incorporation of anactive ingredient in this manner can afford a homogeneous distributionof the additive and result in superior and sustained performancecompared to a pre-made dispersions. An additional benefit of thisintimate incorporation of the bioactive agent is apparent in films thatare prepared using these latices, which are observed to be substantiallytransparent. This feature highlights the highly homogeneous assimilationof the bioactive agent into the latex particles and how this uniformdistribution can provide useful properties for applications such astransparent bioactive films and the like, even in relatively highconcentrations such as up to about 20 percent to about 25 percent.

Other Additives

In another aspect of this disclosure, the latex provided herein can alsoinclude other additives to improve the physical and/or mechanicalproperties of the polymer, the selection of which are known to oneskilled in the art. Such additives include, for example, processing aidsand performance aids, including but are not limited to, cross-linkingagents, natural or synthetic binders, plasticizers, softeners,foam-inhibiting agents, froth aids, flame retardants, dispersing agents,pH-adjusting components, sequestering or chelating agents, or otherfunctional components, or any suitable combination thereof.

Exemplary Substrates and Applications for Bioactive Anionic PolymerLatices

The deposition of the latex polymer coatings of this disclosure on anynumber of different substrates, such as textiles, metal, cellulosicmaterials, plastics, and the like, can impart desired end-useperformance properties to those materials, and therefore tailor thesubstrates for a range of applications. For example, in one aspect, thepresent disclosure provides a treated fibrous material which cancomprise at least one fiber and at least one bioactive anionic polymerlatex as provided herein. In one aspect, the treated fibrous materialcan comprise at least one fiber and at least one bioactive anionicpolymer latex deposited on, or associated with, the at least one fiber.If desired, the bioactive anionic polymer can be applied to the fiber inthe form of a powder, or the polymer composition can be deposited on thefiber by any suitable method known to the skilled artisan.

As used herein, the term “fiber” is intended to be broadly construed andcan include single or multiple filaments that can be present in avariety of ways. It should be appreciated that only a single fiber canbe treated with the bioactive anionic polymer latex of the invention ifso desired. Fibers that can be used in conjunction with this inventioncan encompass natural fibers, synthetic fibers, or any combination ormixture thereof. Natural fibers include, but are not limited to, animalfibers (for example, silk and wool); mineral fibers (for example,asbestos); and vegetable-based fibers (for example, cotton, flax, jute,and ramie). Synthetic fibers include, but are not limited to, those madefrom polymers such as polyamides, polyesters, acrylics, and polyolefins.Other examples of fibers include, but are not limited to, rayon andinorganic substances extruded in fibrous form such as glass, boron,boron carbide, boron nitride, carbon, graphite, aluminum silicate, fusedsilica, and metals such as steel. In another aspect, cellulosic or woodfibers also can be treated with the bioactive anionic polymer latex ofthe invention if so desired. Recycled fibers using any suitable fibersuch as the above materials may also be employed. Any mixture of fiberscan be treated with the bioactive anionic polymer latex of the inventionif so desired.

The treated fibrous material can, in another aspect, have at least oneother polymeric layer deposited on the fiber so as to form a compositefibrous structure, thus multiple polymeric layers of various types canbe used if desired. For example, anionic polymer latices may bedeposited on the treated fibrous material to enhance specific propertiesof the treated fibrous material. In another aspect, the fibrous materialcan be treated in a sequential fashion using, alternately, bioactiveanionic polymer latices and cationic polymer latices, to form multiplelayered structure. While not intending to be bound by theory, it isthought that simple coulombic interactions between anionic and cationicpolymers enhance the stability of such structures, leading to treatedfibrous materials that are robust. Layers of various other non-bioactivepolymers can be employed similarly, for example, deposited on theanionic polymer latex which is present on the fibrous material to form acomposite structure. In this fashion, unique layering architecture canbe constructed with specially modified surfaces in accordance with thisinvention.

In a further aspect, the present invention also provides an article ofmanufacture comprising a substrate and a bioactive anionic polymer latexdeposited or positioned thereon, as provided herein. For the purposes ofthis disclosure, the term “substrate” is intended to be construed andinterpreted broadly to include all those formed from inorganicmaterials, organic materials, composites thereof, mixtures thereof, orany type combination thereof. For example, the substrate can encompass,but is not limited to, paper, composites, fibers, fillers, pigments, andthe like, as well as other organic and inorganic materials.

In one aspect of this invention, as disclosed herein, a fibroussubstrate can be employed. The term “fibrous substrate” is also intendedto be construed and interpreted broadly to include at least all thefibers, woven textiles, and non-woven textiles disclosed herein. Thus,the fibrous substrate may be present, for example, in the form of a web,a yarn, a fabric, a textile substrate, and the like. Further examples offibrous substrates include, but are not limited to, natural fibers suchas cotton and wool to synthetic fibers such as nylon, acrylics,polyesters, urethanes, and the like. Known application processes can beused to apply the bioactive anionic polymer latex, such as rod/knifecoating, impregnation, back coatings, printing, as pretreatments onindividual fibers, or as a finished good. Also as used herein, the term“textile substrate” can be defined according to its use in U.S. Pat. No.5,403,640 to Krishnan et al., the disclosure of which is incorporatedherein by reference in its entirety. In this aspect, for example,“textile substrate” can encompass a fiber, a web, a yarn, a thread, asliver, a woven fabric, a knitted fabric, a non-woven fabric, anupholstery fabric, a tufted carpet, a pile carpet, and the like,including any combination thereof, formed from any of the fibersdescribed herein.

The bioactive anionic latex composition of this invention also can beapplied to a wide variety of plastic or rubber substrates. Examples ofsuch materials include, but are not limited to, commodity moldedthermoplastics such as polyolefins; engineering thermoplastics such aspolysulfones, acetals, polycarbonates, and the like; thermosets such asepoxies, urethanes, and related materials; and as extruded or blownfilms. The polymer could be applied as a coating on the surface byrod/knife coating, spray, dipping, as a laminate coating during theextrusion process, or as a coating applied in the mold during themolding process. Rubber products would include sheets, extruded/moldedarticles, composites, and the like. In another aspect, the bioactiveanionic latex compositions of this invention also can be deployed insolid form. In this aspect, for example, the inventive latices can becoagulated or spray dried to provide the solid bioactive anionic latex,which can be employed in solid form as an additive in plastic products,in processes such as extrusion or blow molding, as additives for variouspolyethylenes, polypropylenes, and the like, and in any number of otherpolymer and plastic applications.

The bioactive anionic latex composition of this invention also can beapplied to wood or metal substrates. In this aspect, suitable substrateswould include all kinds of natural and engineered wood substrates.Suitable metal substrates would include both metals and metal alloys,such as carbon steel, stainless steel, and including solid steel bars,sheets, coils, ropes, and such, wherein the composition is applied as acoating by one of the numerous processes such as spraying dipping,brushing, roller coating, and related methods.

In this context, an article of manufacture comprising a substrate and abioactive anionic polymer latex deposited or positioned thereon can bemade in accordance with standard procedures known to one of ordinaryskill in the relevant art. The article of manufacture can have, inanother aspect, at least one other polymeric layer deposited thereon soas to form a composite structure, thus multiple polymeric layers ofvarious types can be used if desired. For example, other layers ofvarious polymers can be deposited on the bioactive anionic polymer latexwhich is present in the article of manufacture to form a compositestructure. In this aspect, deposition of a bioactive anionic latex canbe followed by the deposition of a cationic latex or other polymers toenhance specific properties of the article of manufacture. Thus,uniquely tailored articles with specially modified surfaces can be madein accordance with the present invention.

In a broader aspect, the present invention also provides a coatedmaterial comprising any material and a bioactive anionic polymer latexdeposited or positioned thereon, wherein additional layers of othermaterials optionally can be used in combination with the bioactiveanionic polymer latex of this invention. As used herein, the term“material” is intended to be used broadly to include, but not be limitedto, any inorganic material, any organic material, any composite thereof,or any combination thereof. Examples of suitable materials include, butare not limited to, a fiber, a filler, a particle, a pigment, compositesthereof, combinations thereof, mixtures thereof, and the like.

A multiple deposition process can also be used to make composite filmsthat have applications in areas other than textiles and fibrousmaterials. In one aspect, for example, the bioactive anionic polymerlatex of this invention can be used to fabricate multilayer elastomericgloves. Cellulosic structures can also be made using the bioactiveanionic polymer latex provided herein including, but not limited to,cellulosic composites and heavy duty cellulosic structures. Examples ofcellulosic composites include, but are not limited to, those compositesrelating to filtration, shoe insoles, flooring felt, gasketing, and thelike. Heavy duty cellulosic structures include, but are not limited to,dunnage bags, industrial wipes, and related structures. In a furtheraspect, the deposition process and bioactive anionic polymer latex ofthis invention also can be used in other technology arts including, butnot limited to, anionic flocculants, wet and dry strength additives forpapermaking, anionic retention aids, cement modifications, dye fixation,redispersible powders, and the like.

The present invention can afford certain advantages as compared toprevious methods used to fabricate bioactive materials. In one aspect,for example, the bioactive anionic latices can be substantiallydeposited on a substrate such that residual bioactive latex does notremain in the processing fluid medium, providing a potential advantagefrom an environmental standpoint. Moreover, bioactive anionic laticescan be preferentially deposited on any substrate that carries a netpositive charge, and deposition can occur in a uniform manner, therebyusing less latex. In this aspect, and while not intending to be bound bytheory, the bioactive anionic latices are thought to be capable offorming substantially uniform monolayers of polymer material on apositively charged substrate, thereby allowing the use of less latex toprovide the desired coverage. Because the bioactive anionic latices canbe formed by existing emulsion polymerization processes, thepolymerization methods advantageously allow for the preparation of highmolecular weight polymers.

In a further aspect, the antimicrobial anionic polymer latices of thisdisclosure can constitute a useful component of filled latex. Manyfillers such as mica or calcium carbonate are negatively charged and canbe difficult to use in large amounts in combination with cationiclatices. Thus, when a filled latex is desired, this invention affords,among other things, an anionic latex polymer that can be used to preparea filled latex, even when relatively high concentrations of fillers areneeded.

As provided herein, the latex composition of the present invention canbe applied to a wide variety of substrates using various techniques thatare well known to one of ordinary skill in the art. As a result, thereare numerous applications for the present invention, many of which areprovided in the following listing. In this aspect, while this listing isnot comprehensive, specific applications include, but are not limitedto: textiles such as residential and commercial carpets or tiles; liquidand air filters for HVAC or vacuum cleaners, or automotive uses; medicalsurgical gowns, drapes, dressings, covers, and the like; pretreatmentfor fibers, printed or dyed fabrics for apparel, furnishings, sheets,towels, and the like; diapers and incontinence articles; interiorautomotive applications such as trim, upholstery, mats, filters, andsuch; upholstery coatings; laminating and bonding adhesives; foams forsound absorbency; foamed articles such as pillows and mattresses;belting or other machinery parts for food handling and the like; tapessuch as masking tapes, surgical tape, industrial tapes, and the like;electrical, industrial, and household cleaning wipes, cloths, andsponges; shoe products such as insoles, box toes, and such; plasticand/or rubber items such as tool handles, tool grips, toys, rubbergloves, sheets, or other articles; machinery housing such as forcomputers, display and diagnostic devices or instrumentation; medicaldevices such as catheters, balloons, tubing, syringes, diagnostic kits,and the like; packaging or product protection, as applied toperishables, computer peripherals, semiconductors, memory chips, CDs,DVDs, and the like; impact modifiers for acrylics, polycarbonates, andsuch; overdips or underdips for gloves such as gloves for clean rooms;breathable films; antipenetrant for fabric supported gloves; cuttingboards; extruded and blown films for packaging; paper products such asvacuum bags, book covers, air filters, liquid filters, wallcoverings,wet and dry wipes, tissues, and such; felt for vinyl floor coverings;molded pulp applications; packaging such as boxes, cartons, moldedarticles, and related items; size press coatings for gift wraps, ink jetmedia, breathable coatings, and the like; wet end additives in paper,tapes, labels for use in masking, surgical applications, general purposeapplications, and such; binders for use in paper; binders for use inwallboard such as gypsum wallboard and the like; adhesives for use intapes, labels, decals, films, book bindings, pressure sensitiveapplications, flexible packaging and laminating adhesive (FPLA), and thelike; inorganic and/or organic materials such as coating orencapsulation of fillers or pigments, construction sealers and grouts,gypsum wallboard coatings or binders, exterior or interior coatings, andthe like; tile adhesives; floor coatings for use in hospitals, cleanrooms, clinics, schools, and related environments; coatings for hospitaland medical environments; ceiling tiles; glass fiber coatings such asglass mats, insulation, filter materials, reinforced composites, andsuch; coatings for air conditioning or refrigeration coils; othercomponents for air conditioning systems, heat exchangers, ionexchangers, process water systems including cooling water treatment,solar-powered units, coated pipes, and the like; kitchen items;components of sanitary equipment; components of water systems; operatorunits of devices such as touch panels; materials used in bathrooms suchas shower curtains, fixtures, toilet items, and even jointing or sealingcompounds; medical devices such as use in coatings for stents, implants,prostheses, catheters, tubing, contact lenses, protective or backingfilms, medical instruments, and other medical devices for providing thesustained action of bioactive agents; articles which are contacted bylarge numbers of people such as telephone handsets, stair rails, doorhandles, window catches, grab straps and grab handles in publicconveyances, and the like; liquid disinfectants and cleaners; personalcare or hygiene products such as shampoos, lotions, creams, hair andskin care products, body wash, cosmetics, toilet items, and the like;hygiene coatings of surfaces other than floors, such as in hospitals,clinics, schools, homes, offices, and the like; hard and porous surfacecoatings as applicable to walls, ceilings, floors, counter tops, and thelike; decorative concrete; wood such as oriented strand board (OSB)coatings; decking and construction materials for coating orimpregnation; composite construction materials; furniture coatings;hygiene coatings such as used in table tops, counter tops, door knobs,door handles, fixtures, and the like; flooring applications such as inlaminates, hardwood flooring, and other composite flooring materials;decorative laminates such as table tops, counter tops, furniture, andthe like; other construction materials such as roofing material, wallmaterial, facades, fencing, or for wood protection applications; marineapplications such as in boat hulls, docks, buoys, drilling platforms, orballast water tanks; metal such as cabinets, door knobs, handles,fixtures, and such; and furniture, coatings as applicable to appliances,original equipment manufacture (OEM), and the like.

In this aspect, the antimicrobial formulations of the invention can beuseful as a biofouling inhibitor, in particular, in cooling circuits. Toprevent damage to cooling circuits by infestation with algae orbacteria, the circuits typically have to be cleaned frequently or beappropriately oversized. In the open cooling systems usually found inpower plants and in chemical plants, the addition of microbiocidalsubstances, such as formalin, is generally not possible. Othermicrobiocidal substances are frequently highly corrosive or form foams,preventing their use in systems of this type. Deposition of bacteria oralgae on components of the system can thus be effectively inhibited.Therefore, the formulations and materials of this invention can be quiteuseful in such applications.

In another aspect, the present invention can also provide a process forsterilizing cooling-water streams or process water systems, by addingantimicrobial formulations in dispersed form to the cooling water. Thedispersed form can be obtained in the preparation process itself, forexample, by emulsion polymerization as detailed herein, but also byprecipitation polymerization, or suspension polymerization, orsubsequently by milling of the antimicrobial polymer obtained by any ofthese methods, for example, in a jet mill.

The antimicrobial latex polymer of this invention can be applied or usedas a coating composition, which can be used for a wide variety ofpurposes in connection with which antimicrobial action is desired. Forexample, in one aspect, the antimicrobial latex polymers disclosedherein can be used in connection with a wide range of insulatingmaterials such as wrapping materials for pipes, which are a particularrisk of bacterial attack. Thus, the materials of the invention areuseful when used in connection with elastomeric insulating materials.Such coating compositions can also be used in connection with industrialinsulation, such as is used for insulating pipelines, examples beingheating pipes, and for insulating valves and ducts. Moreover,antimicrobial latices disclosed herein can be used in conjunction withall thermal and/or acoustic insulations and related insulating materialsfor numerous end applications. The latices provided herein can also beused in conjunction with industrial foams and foam materials assubstrates for antimicrobial coatings. Such coatings comprising theantimicrobial latices disclosed herein also can be used as coatings forair-conditioning plants, condensers, refrigerators and otherrefrigeration units, and also parts thereof, and also for coatingcompositions as paints for marine craft and for wood preservation.Coatings comprising the antimicrobial latices of this disclosure canalso be employed as the coating of substrates such as metal, plastic, orceramic, in hygiene installations, hospitals, or in the food industry,or any articles involving frequent contact of any type which may easilytransmit infection pathogens, such as door handles, sanitary fittings,switches, and grips. In the case of such coatings the use of a coatingcomposition in the form of powder coatings can be advantageous.

Applications of Antimicrobial Latices to Medical Devices

The term “medical device” as used herein refers to any material, naturalor artificial, that is inserted into a mammal. Particular medicaldevices suited for application of the antimicrobial latices andcompositions of this invention include, but are not limited to,peripherally insertable central venous catheters, dialysis catheters,long term tunneled central venous catheters, long term non-tunneledcentral venous catheters, peripheral venous catheters, short-termcentral venous catheters, arterial catheters, pulmonary artery Swan-Ganzcatheters, urinary catheters, artificial urinary sphincters, long termurinary devices, urinary dilators, urinary stents, other urinarydevices, tissue bonding urinary devices, penile prostheses, vasculargrafts, vascular catheter ports, vascular dilators, extravasculardilators, vascular stents, extravascular stents, wound drain tubes,hydrocephalus shunts, ventricular catheters, peritoneal catheters,pacemaker systems, small or temporary joint replacements, heart valves,cardiac assist devices and the like and bone prosthesis, jointprosthesis and dental prosthesis.

In one aspect, the medical devices that can be used in conjunction withthe bioactive anionic latices of this invention include, but are notlimited to, non-metallic materials such as thermoplastic or polymericmaterials. Examples of such materials include rubber, plastic,polyethylene, polyurethane, silicone, GORTEX™ (polytetrafluoroethylene),DACRON™ (polyethylene tetraphthalate), polyvinyl chloride, TEFLON™(polytetrafluoroethylene), elastomers, nylon and DACRON™ sealed withgelatin, collagen or albumin. The amount of each bioactive anionic latexused to coat the medical device varies to some extent, but is at least asufficient amount to form an effective concentration to inhibit thegrowth of bacterial and fungal organisms.

The antimicrobial latices can be used alone or in a combinationcomprising two or more antimicrobial latices. Each antimicrobial latexcan comprise one or more antimicrobial components as provided herein.Any application or use disclosed herein can further encompass the use ofat least one bioactive latex in conjunction with at least one otherantimicrobial agent that can be dispersed throughout the surface of themedical device. The amount of each bioactive latex and eachantimicrobial agent used to impregnate the medical device varies to someextent, but is at least of an effective concentration to inhibit thegrowth of bacterial and fungal organisms.

In one aspect, the antimicrobial agent can be selected from anantibiotic, an antiseptic, a disinfectant, or any combination thereof.In another aspect, the antimicrobial agent can be an antibioticincluding, but not limited to, penicillins, cephalosporins, carbepenems,other beta-lactam antibiotics, aminoglycosides, macrolides,lincosamides, glycopeptides, tetracylines, chloramphenicol, quinolones,fucidins, sulfonamides, trimethoprims, rifamycins, oxalines,streptogramins, lipopeptides, ketolides, polyenes, azoles,echinocandins, or any combination thereof.

In one aspect, at least one drug can be applied to a medical deviceusing bioactive latices provided herein, and used in combinations withdrugs that can adhere to, rather than be encapsulated by, the bioactivelatices. For example, a anionic antimicrobial latex coating can beapplied as a coating to a medical device that can have an ionic charge.Subsequently, drugs having a complimentary charge can be applied to, andcan bind to, the charged coating applied to the surface of device whenthe charged coating and the drug are exposed to one another. Thestrength of bonding between the drug and the coating can be used toinfluence how readily the drug can be released from the surface of thedevice. In one aspect, this disclosure provides for delivering animplant or medical device having this drug delivery feature to aselected anatomical site. In this aspect, typically drugs that areuseful include, but are not limited to, antimicrobials and antibioticssuch as neomycin and sulfa drugs, anti-inflammatory agents such assteroidal or non-steroidal anti-inflammatory agents, or combinationsthereof.

Applications of Bioactive Anionic Polymer Latices in WallboardManufacture

Wallboard is typically produced by enclosing a core of an aqueous slurryprepared using calcium sulfate hemihydrate, referred to as calcinedgypsum, and other materials between two large sheets of wallboard coverpaper. After the gypsum slurry has set and has been dried, the formedsheet is cut into standard sizes. Thus, the core of wallboard can beconsidered to be prepared by combining a “dry” portion and a “wet” oraqueous portion which is then situated between two sheets of coverpaper, and which sets or hardens.

A major “dry” ingredient of the gypsum wallboard core is calcium sulfatehemihydrate, commonly referred to as calcined gypsum or stucco, which isprepared by drying, pulverizing, and calcining natural gypsum rock(calcium sulfate dihydrate). The drying step simply removes any freemoisture that is not chemically bound in the rock, while calciningliberates a portion of the chemically bound water molecules. As aresult, calcined gypsum has the desirable property of being chemicallyreactive with water, and will set rather quickly when the two arecontacted and the calcium sulfate hemihydrate is rehydrated to itsdihydrate state. In addition to calcium sulfate hemihydrate, the dryingredients can include a wide range of addititives, such as setretarders, set accelerators, antidesiccants, stabilizers, starch, and/orother additives that can be useful in the production process or thefinal wallboard properties.

In addition to including water, the “wet” portion of the wallboard corecomposition comprises paper pulp. In one aspect, the wet portion of thewallboard core composition typically, though not necessarily, includes afirst wet component and a second wet component. The first wet componentcan be referred to as a paper pulp solution, and includes a mixture ofwater, paper pulp, optionally one or more fluidity-increasing agents,and optionally a set retarder. The paper pulp solution provides a majorportion of the water that forms the gypsum slurry of the corecomposition. The second wet component can include a compositioncomprising strengthening agents, foaming agents, surfactants, otherconventional additives, or any combination thereof. Any wet componentgenerally, or the first wet component and second wet component, can becombined with the dry portion of the gypsum wallboard core in any orderor manner.

In another aspect, the face paper and backing paper cover sheets used inwallboard manufacture are typically multi-ply paper manufactured fromre-pulped newspapers. Both the face paper and the backing paper usuallyhave an inner ply (typically unsized) which contacts the core slurrysuch that gypsum crystals can grow up to or into the inner ply. Thisgypsum crystal-paper interaction constitutes one principal form ofbonding between the core slurry and the cover sheet. The middle pliesare usually sized and an outer ply is more heavily sized and can betreated to control the absorption of paints and scalers. Both coversheets typically have sufficient permeability to allow for water vaporto pass through during the downstream board drying process. These andrelated methods for the production of gypsum wallboard generally aredescribed, for example, in Michelsen, T. “Building Materials (Survey),”Kirk-Othmer Encyclopedia of Chemical Technology, (1992 4^(th) ed.), vol.4, pp. 618-619, the disclosure of which is hereby incorporated herein byreference.

One aspect of this invention provides an antimicrobial wallboard articleof manufacture comprising at least one bioactive latex polymer disclosedherein, and also provides a process for making an antimicrobial gypsumwallboard comprising at least one bioactive latex polymer. In thisaspect, the bioactive latex polymer can be used in any component of thewallboard, that is, as a component of the gypsum wallboard core, thefirst cover sheet, the second cover sheet, or any combination thereof.Thus, this method and article comprise adding at least one antimicrobiallatex to the wallboard or any component thereof, at levels sufficientlyeffective against microbes, therefore, a bioactive latex is an optionalingredient of each wallboard component. Moreover, the at least onebioactive latex polymer can be used in any form, such as an emulsion, adispersion, or in solid form, as disclosed herein. Thus in a furtheraspect, this disclosure provides for adding the at least one bioactivelatex polymer in a finishing step such as coating, spraying, painting,or the like.

In a further aspect, this invention also provides for using bioactiveanionic polymer latices as binder or coating materials that can becombined with paper pulp used to prepare the face paper and backingpaper cover sheets in wallboard manufacture. In this aspect, either orboth sheets of the wallboard cover paper can comprise at least onebioactive anionic polymer latex disclosed herein, which can be the sameor can be different. These bioactive anionic latices can be used toprepare the inner, middle, or outer plies of the cover sheets, or anycombination thereof. Moreover, any combination of cover sheets in whichthe first, the second, or both covers sheets comprise antimicrobialcomponents can be used with a gypsum slurry that comprises at least onebioactive anionic polymer latex, or with a gypsum slurry that does notcomprise at least one bioactive anionic polymer latex.

Thus in one aspect, this disclosure provides a method of making anantimicrobial wallboard comprising:

a) forming a slurry comprising calcium sulfate hemihydrate, water, paperpulp, and optionally at least one first bioactive anionic polymer latex;

b) depositing the slurry onto a first cover sheet optionally comprisingat least one second bioactive anionic polymer latex; and

c) applying a second cover sheet optionally comprising at least onethird bioactive anionic polymer latex on top of the deposited slurry;and

d) drying the resulting wallboard;

wherein at least one of the slurry, the first cover sheet, or the secondcover sheet comprises at least one bioactive aionic polymer latex; and

wherein the at least one first bioactive anionic polymer latex, the atleast one second bioactive anionic polymer latex, and the at least onethird bioactive anionic polymer latex are the same or are different.

Thus, the at least one first, the at least one second, and at least onethird bioactive anionic polymer latices are selected independently ofeach other. Any of the bioactive anionic polymer latices or combinationsof bioactive anionic polymer latices disclosed herein can be employed inany of the antimicrobial wallboard components.

Accordingly, this invention also provides an antimicrobial wallboardcomprising:

a) a gypsum sheet optionally comprising at least one first bioactiveanionic polymer latex;

b) a first cover sheet disposed on one side of the gypsum sheet andoptionally comprising at least one second bioactive anionic polymerlatex; and

c) a second cover sheet disposed on the opposite side of the gypsumsheet and optionally comprising at least one third bioactive anionicpolymer latex;

wherein at least one of the gypsum sheet, the first cover sheet, or thesecond cover sheet comprise at least one bioactive anionic polymerlatex; and

wherein the at least one first bioactive anionic polymer latex, the atleast one second bioactive anionic polymer latex, and the at least onethird bioactive anionic polymer latex are the same or are different.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed. All publications and patents mentioned herein areincorporated herein by reference for the purpose of describing anddisclosing, for example, the constructs and methodologies that aredescribed in the publications, which might be used in connection withthe presently described invention. The publications discussed herein areprovided solely for their disclosure prior to the filing date of thepresent application. Nothing herein is to be construed as an admissionthat the inventors are not entitled to antedate such disclosure byvirtue of prior invention.

When Applicants disclose or claim a range of any type, for example arange of temperatures, a range of concentrations, a range of numbers ofatoms, a weight percent, or the like, Applicants' intent is to discloseor claim individually each possible number that such a range couldreasonably encompass, as well as any sub-ranges and combinations ofsub-ranges encompassed therein. Thus, when the Applicants disclose orclaim a chemical moiety having a certain number of carbon atoms,Applicants' intent is to disclose or claim individually every possiblenumber, sub-range, and combination of sub-ranges that such a numberrange could encompass, consistent with the disclosure herein. Forexample, the disclosure that R is selected from an alkyl group having upto 12 carbon atoms, or in alternative language a C₁ to C₁₂ alkyl group,as used herein, refers to an R group that can be selected independentlyfrom an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12carbon atoms, as well as any range between these two numbers for examplea C₃ to C₈ alkyl group, and also including any combination of rangesbetween these two numbers for example a C₃ to C₅ and C₇ to C₁₀ alkylgroup. Thus, Applicants retain the right to replace the terminology suchas “group having up to 12 carbon atoms” with any individual number thatsuch a range could reasonably encompass, as well as any sub-ranges andcombinations of sub-ranges encompassed therein. In another example, bythe disclosure that the molar ratio typically spans the range from about0.1 to about 1.0, Applicants intend to recite that the molar ratio canbe selected from about 0.1:1, about 0.2:1, about 0.3:1, about 0.4:1,about 0.5:1, about 0.6:1, about 0.7:1, about 0.8:1, about 0.9:1, orabout 1.0:1, as well as any sub-ranges and combinations of sub-rangesencompassed therein. Similarly, the disclosure that a particular weightpercent can be from about 80 percent to about 90 percent by weight,Applicants' intend to recite that the weight percent can be about 80percent, about 81 percent, about 82 percent, about 83 percent, about 84percent, about 85 percent, about 86 percent, about 87 percent, about 88percent, about 89 percent, or about 90 percent, by weight.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that may be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, additives, compounds, monomers,surfactants, structures, and the like, or any groups thereof, or anyindividual members of a claimed group, if for any reason Applicantschoose to claim less than the full measure of the disclosure, forexample, to account for a reference that Applicants may be unaware of atthe time of the filing of the application.

For any particular chemical compound disclosed herein, any generaldisclosure or structure presented also encompasses all isomers, such asconformational isomers, regioisomers, stereoisomers, and the like, thatcan arise from a particular set of substituents. The general structurealso encompasses all enantiomers, diastereomers, and other opticalisomers whether in enantiomeric or racemic forms, as well as mixtures ofstereoisomers, as the context requires.

The present invention is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort can be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

In the following examples, unless otherwise specified, the reagents wereobtained from commercial sources. General procedures, including generalsynthetic testing procedures for polymer latices, are provided in U.S.Patent Application Publication Numbers 2005/0065284 and 2005/0003163, toKrishnan, each disclosure of which is incorporated herein by referencein its entirety.

EXAMPLE 1 Bioactive Anionic Latex Preparation

A one-liter polymerization reactor can be charged with the followingingredients: about 270 g of water; about 6 g of the nonionic surfactantABEX™ 2525 (Rhodia); about 2.7 g of an anionic surfactant DOWFAX™ 2A1(Dow Chemical Company), and about 3 g of methacrylic acid. The reactorcontents can be deoxygenated by subjecting the reactor to severalvacuum/N₂ fill cycles.

The following reactor feeds can be prepared:

1) An aqueous monomer feed containing about 150 g of water, about 6 g ofmethoxy polyethyleneglycolmethacrylate (MPEG 550 from Cognis), about 4.5g of methacrylic acid, about 1.3 g of DOWFAX™ 2A1, and about 6 g ofABEX™ 2525. The total feed time into the reactor is 5 hours;

2) A non-aqueous monomer feed containing about 153 g of butyl acrylate,about 132 g of methyl methacrylate, and about 64 g of the bioactiveagent. The total feed time for this feed is 5 hours. The bioactive agentcan be introduced into this feed after about a 3-hour time period. Thus,the non-aqueous monomer feed during the first 3 hours contains onlybutyl acrylate and methyl methacrylate; and

3) An initiator feed that can contain about 30 g of water and about 2.10g of an initiator, V-501™ (Wako Chemical). The total feed time is about5.5 hours. A few drops of ammonia can be added to aid in the dissolutionof the initiator, if needed.

To the initial reactor charge can be added 10% of the non-aqueousmonomer feed, which contains only the two monomers methyl methacrylateand butyl acrylate, as the bioactive agent is not introduced into themonomer until 3 hours into the feed. The temperature of the reactor thencan be raised to about 165° F. and when this set point is reached, anoriginal initiator solution (separate from the initiator feed describedabove) containing about 3 g of water and about 0.30 g of V-501 can beinjected into the reactor. The reactor contents are maintained at thistemperature for about 30 minutes before the feeds are started.

When addition of the feeds is completed, the reaction is continued untilmost (greater than about 98%) of the monomers have reacted. The reactorcontents then can be cooled down and the vacuum stripped to removeunreacted monomers and to raise the solids concentration to about 42-43percent by weight. If necessary, the pH of the latex can be adjusted toaround 6.0 to about 7.0 before stripping the reaction volatiles.

EXAMPLE 2 Bioactive Anionic Latex Prepared by Late Introduction of theBioactive Agent

An emulsion polymerization reaction can be conducted according to thedetails provided in Example 2, except that an approximately 32 g-sampleof bioactive component can be introduced into the non-aqueous monomerfeed after about 4 hours, rather than 3 hours, of the 5-hour non-aqueousmonomer feed.

In the specification, typical embodiments of the invention have beendisclosed and, although specific terms are employed, they are used in ageneric and descriptive sense and not for purposes of limitation. Thisinvention is further illustrated and described by the appended claims,however, it should be clearly understood that resort can be had tovarious other embodiments, aspects, modifications, and equivalents tothose disclosed in the claims, which, after reading the descriptionherein, may suggest themselves to one of ordinary skill in the artwithout departing from the spirit of the present invention or the scopeof these claims. The following claims are provided to ensure that thepresent application meets all statutory requirements as a priorityapplication in all jurisdictions and shall not be construed as settingforth the full scope of the present invention.

1. A bioactive anionic polymer latex comprising: a) a latex polymercomprising the polymerization product of: i) at least one ethylenicallyunsaturated first monomer; and ii) optionally, at least oneethylenically unsaturated second monomer that is anionic or a precursorto an anion; b) at least one bioactive component at least partiallyencapsulated within the latex polymer; and c) optionally, at least onesterically bulky component incorporated into the latex polymer.
 2. Thebioactive anionic polymer latex according to claim 1, wherein the atleast one ethylenically unsaturated first monomer is selectedindependently from a vinyl aromatic monomer, a halogenated ornon-halogenated olefin monomer, an aliphatic conjugated diene monomer, anon-aromatic unsaturated mono-carboxylic ester monomer, an unsaturatedalkoxylated monoester or diester monomer, an unsaturated diester of anacid anhydride monomer, a nitrogen-containing monomer, anitrile-containing monomer, a cyclic or an acyclic amine-containingmonomer, a branched or an unbranched alkyl vinyl ester monomer, an arylvinyl ester monomer, a halogenated or a non-halogenatedalkyl(meth)acrylate monomer, a halogenated or a non-halogenatedaryl(meth)acrylate monomer, a carboxylic acid vinyl ester, an aceticacid alkenyl ester, a carboxylic acid alkenyl ester, a vinyl halide, avinylidene halide, or any combination thereof, any of which having up to20 carbon atoms.
 3. The bioactive anionic polymer latex according toclaim 1, wherein the at least one ethylenically unsaturated firstmonomer is selected independently from styrene, para-methyl styrene,chloromethyl styrene, vinyl toluene, ethylene, butadiene,methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate,butyl(meth)acrylate, pentyl(meth)acrylate, glycidyl(meth)acrylate,isodecyl(meth)acrylate, lauryl(meth)acrylate, (meth)acrylonitrile,(meth)acrylamide, N-methylol(meth)acrylamide,N-(isobutoxymethyl)(meth)acrylamide, vinyl neodecanoate, vinylversatate, vinyl acetate, a C₃-C₈ alkyl vinylether, a C₃-C₈ alkoxy vinylether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidenefluoride, trifluoroethylene, tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene,perfluorobutyl ethylene, a perfluorinated C₃-C₈ alpha-olefin, afluorinated C₃-C₈ alkyl vinylether, a perfluorinated C₃-C₈ alkylvinylether, a perfluorinated C₃-C₈ alkoxy vinyl ether, or anycombination thereof.
 4. The bioactive anionic polymer latex according toclaim 1, wherein the at least one ethylenically unsaturated secondmonomer is selected independently from a monomer based on the half esterof an unsaturated dicarboxylic acid monomer, an unsaturated mono- ordicarboxylic acid monomer, a sulfate-containing monomer, asulfonate-containing monomer, a phosphate-containing monomer, aphosphonate-containing monomer, an unsaturated anhydride, a monoester ofan acid anhydride, or any combination thereof, any of which having up to20 carbon atoms.
 5. The bioactive anionic polymer latex according toclaim 1, wherein the at least one ethylenically unsaturated secondmonomer is selected independently from (meth)acrylic acid, maleic acid,maleic anhydride, 2-sulfoethyl(meth)acrylate, styrene sulfonate,2-acrylamido-2-methylpropane sulfonic acid, monomethyl maleate, itaconicacid, itaconic anhydride, fumaric acid, or any combination thereof. 6.The bioactive anionic polymer latex according to claim 1, wherein the atleast one sterically bulky component is selected independently from atleast one sterically bulky ethylenically unsaturated third monomer, atleast one sterically bulky polymer, or any combination thereof.
 7. Thebioactive anionic polymer latex according to claim 1, wherein the atleast one sterically bulky component is at least one sterically bulkyethylenically unsaturated third monomer selected independently from: a)CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), wherein R^(1A), R^(2A), andR^(3A) are selected independently from H or an alkyl group having from 1to 6 carbon atoms, inclusive, and m is an integer from 1 to 30,inclusive; b) CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B))_(n)R^(3B),where R^(1B), R^(2B), and R^(3B) are selected independently from H or analkyl group having from 1 to 6 carbon atoms, inclusive, and n and p areintegers selected independently from 1 to 15, inclusive; c)CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), wherein R^(1C),R^(2C), and R^(3C) are selected independently from H or an alkyl grouphaving from 1 to 6 carbon atoms, inclusive, and q and r are integersselected independently from 1 to 15, inclusive; or d) any combinationthereof.
 8. The bioactive anionic polymer latex according to claim 1,wherein the at least one sterically bulky component is at least onesterically bulky ethylenically unsaturated third monomer selectedindependently from: a) CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), whereinR^(1A), R^(2A), and R^(3A) are selected independently from H or methyl,and m is an integer from 1 to 10, inclusive; b)CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B), wherein R^(1B),R^(2B), and R^(3B) are selected independently from H or methyl, and nand p are integers selected independently from 1 to 10, inclusive; c)CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), wherein R^(1C),R^(2C), and R^(3C) are selected independently from H or methyl, and qand r are integers selected independently from 1 to 10, inclusive; or d)any combination thereof.
 9. The bioactive anionic polymer latexaccording to claim 1, wherein the at least one sterically bulkycomponent is selected independently from: an alkoxylated monoester of adicarboxylic acid; an alkoxylated diester of a dicarboxylic acid; aalkyl allyl sulfosuccinate salt; a vinyl sulfonate salt; apolyoxyethylene alkylphenyl ether; a polyoxyethylene alkylphenyl etherammonium sulfate; a polymerizable surfactant; or any combinationthereof.
 10. The bioactive anionic polymer latex according to claim 1,wherein the at least one sterically bulky component is at least onesterically bulky polymer selected independently from polyvinyl alcohols,polyvinyl pyrollidone, hydroxyethyl cellulose, or any combinationthereof.
 11. The bioactive anionic polymer latex according to claim 1,wherein the at least one bioactive component is selected independentlyfrom undecylenic acid; undecylenic alcohol; the reaction product ofundecylenic acid with hydroxylethyl(meth)acrylate or polyethyleneglycol(meth)acrylate; the reaction product of undecylenic alcohol with(meth)acrylic acid, maleic anhydride, or itaconic acid; or anycombination thereof.
 12. The bioactive anionic polymer latex accordingto claim 1, wherein the at least one bioactive component is selectedindependently from copper, copper salts, silver, silver salts, zinc,zinc salts, silver oxide, zinc oxide, chlorhexidine, chlorhexidinegluconate, glutaral, halazone, hexachlorophene, nitrofurazone,nitromersol, povidone-iodine, thimerosol, C₁- to C₅-parabens,hypochlorite salts, clofucarban, clorophene, poloxamer-iodine,phenolics, mafenide acetate, aminacrine hydrochloride, quaternaryammonium salts, oxychlorosene, metabromsalan, merbromin, dibromsalan,glyceryl laurate, pyrithione salts, sodium pyrithione, zinc pyrithione,(dodecyl)(diethylenediamine)glycine, (dodecyl)(aminopropyl)glycine,phenol, m-cresol, n-cresol, p-cresol, o-phenyl-phenol, resorcinol, vinylphenol, polymeric guanidines, polymyxins, bacitracin, circulin,octapeptins, lysozmye, lysostaphin, cellulytic enzymes, vancomycin,ristocetin, actinoidins, avoparcins, tyrocidin A, gramicidin S, polyoxinD, tunicamycin, neomycin, streptomycin, or any combination thereof. 13.The bioactive anionic polymer latex according to claim 1, wherein the atleast one bioactive component is selected independently fromazaconazole, biternatol, bromuconazole, cyproconazole, diniconazole,fenbuconazole, flusilazole, flutnafol, imazalil, imibenconazole,metconazole, paclobutrazol, perfuazoate, penconazole, simeconazole,triadimefon, triadimenol, uniconazole, mancozeb, maneb, metiram, zineb,fludioxonil, fluquinconazole, difenoconazole,4,5-dimethyl-N-(2-propenyl)-2-(trimethylsilyl)-3-thiophenecarboxamide(sylthiopham),hexaconazole, etaconazole, triticonazole, flutriafol, epoxiconazole,bromuconazote, tetraconazole, myclobutanil, bitertanol, pyremethanil,cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl, azoxystrobin,ZEN90160™, fenpiclonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl,orfurace, oxadixyl, carboxin, prochloraz, triflumizole, pyrifenox,acibenzolar-S-methyl, chlorothalonil, cymoxanil, dimethomorph,famoxadone, quinoxyfen, fenpropidine, spiroxamine, triazoxide,BAS50001F™, hymexazole, pencycuron, fenamidone, guazatine, benomyl,captan, carbendazim, capropamid, ethirimol, flutolanil,fosetyl-aluminum, fuberidazole, hymexanol, kasugamycin,iminoctadine-triacetate, ipconazole, iprodione, mepronil, metalaxyl-M(mefenoxam), nuarimol, oxine-copper, oxolinic acid, perfurazoate,propamocarb hydrochloride, pyroquilon, quintozene, silthiopham, MON™65500, tecnazene, thiabendazole, thifluzamide, thiophenate-methyl,thiram, tolclofos-methyl, triflumizole, or any combination thereof. 14.The bioactive anionic polymer latex according to claim 1, comprisingfrom about 0.01% to 100% by weight of the ethylenically unsaturatedfirst monomer, based on the total monomer weight.
 15. The bioactiveanionic polymer latex according to claim 1, comprising from 0% to about99.99% by weight of the ethylenically unsaturated second monomer, basedon the total monomer weight.
 16. The bioactive anionic polymer latexaccording to claim 1, comprising from about 0.01% to about 40% by weightbioactive additive, based on the total monomer weight.
 17. The bioactiveanionic polymer latex according to claim 1, comprising from 0% to about25% by weight sterically bulky component, based on the total monomerweight.
 18. The bioactive anionic polymer latex according to claim 1,further comprising a nonionic surfactant.
 19. The bioactive anionicpolymer latex according to claim 1, wherein the latex polymer issubstantially devoid of anionic surfactants.
 20. A coating comprisingthe bioactive anionic polymer latex according to claim
 1. 21. An articlecomprising the bioactive anionic polymer latex according to claim
 1. 22.A method of making a bioactive anionic polymer latex comprisinginitiating an emulsion polymerization of an aqueous compositioncomprising, at any time during the emulsion polymerization: a) at leastone ethylenically unsaturated first monomer; b) optionally, at least oneethylenically unsaturated second monomer that is anionic or a precursorto an anion; c) at least one anionic surfactant; d) at least onebioactive component; e) at least one free-radical initiator; f)optionally, at least one sterically bulky ethylenically unsaturatedthird monomer; g) optionally, at least one sterically bulky polymer; andh) optionally, at least one nonionic surfactant.
 23. The method ofmaking a bioactive anionic polymer latex according to claim 22, whereinthe method is a semi-continuous process, and wherein at least onebioactive component is dissolved in the monomer feed at any time duringthe emulsion polymerization.
 25. The method of making a bioactiveanionic polymer latex according to claim 22, wherein the method is abatch process, and wherein the at least one bioactive component ispresent in the seed stage of the emulsion polymerization.
 26. The methodof making a bioactive anionic polymer latex according to claim 22,wherein the aqueous composition components and the at least onebioactive component are provided as a dispersion prior to initiating theemulsion polymerization.
 27. The method of making a bioactive anionicpolymer latex according to claim 22, wherein the at least oneethylenically unsaturated first monomer is selected independently from avinyl aromatic monomer, a halogenated or non-halogenated olefin monomer,an aliphatic conjugated diene monomer, a non-aromatic unsaturatedmono-carboxylic ester monomer, an unsaturated alkoxylated monoester ordiester monomer, an unsaturated diester of an acid anhydride monomer, anitrogen-containing monomer, a nitrile-containing monomer, a cyclic oran acyclic amine-containing monomer, a branched or an unbranched alkylvinyl ester monomer, an aryl vinyl ester monomer, a halogenated or anon-halogenated alkyl(meth)acrylate monomer, a halogenated or anon-halogenated aryl(meth)acrylate monomer, a carboxylic acid vinylester, an acetic acid alkenyl ester, a carboxylic acid alkenyl ester, avinyl halide, a vinylidene halide, or any combination thereof, any ofwhich having up to 20 carbon atoms.
 28. The method of making a bioactiveanionic polymer latex according to claim 22, wherein the at least oneethylenically unsaturated first monomer is selected independently fromstyrene, para-methyl styrene, chloromethyl styrene, vinyl toluene,ethylene, butadiene, methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate,glycidyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate,(meth)acrylonitrile, (meth)acrylamide, N-methylol(meth)acrylamide,N-(isobutoxymethyl)(meth)acrylamide, vinyl neodecanoate, vinylversatate, vinyl acetate, a C₃-C₈ alkyl vinylether, a C₃-C₈ alkoxy vinylether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidenefluoride, trifluoroethylene, tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoro-ethylene,perfluorobutyl ethylene, a perfluorinated C₃-C₈ alpha-olefin, afluorinated C₃-C₈ alkyl vinylether, a perfluorinated C₃-C₈ alkylvinylether, a perfluorinated C₃-C₈ alkoxy vinyl ether, or anycombination thereof.
 29. The method of making a bioactive anionicpolymer latex according to claim 22, wherein the at least oneethylenically unsaturated second monomer is selected independently froma monomer based on the half ester of an unsaturated dicarboxylic acidmonomer, an unsaturated mono- or dicarboxylic acid monomer, asulfate-containing monomer, a sulfonate-containing monomer, aphosphate-containing monomer, a phosphonate-containing monomer, anunsaturated anhydride, a monoester of an acid anhydride, or anycombination thereof, any of which having up to 20 carbon atoms.
 30. Themethod of making a bioactive anionic polymer latex according to claim22, wherein the at least one ethylenically unsaturated second monomer isselected independently from (meth)acrylic acid, maleic acid, maleicanhydride, 2-sulfoethyl(meth)acrylate, styrene sulfonate,2-acrylamido-2-methylpropane sulfonic acid, monomethyl maleate, itaconicacid, itaconic anhydride, fumaric acid, or any combination thereof. 31.The method of making a bioactive anionic polymer latex according toclaim 22, wherein the at least one sterically bulky component isselected independently from at least one sterically bulky ethylenicallyunsaturated third monomer, at least one sterically bulky polymer, or anycombination thereof.
 32. The method of making a bioactive anionicpolymer latex according to claim 22, wherein the at least one stericallybulky component is at least one a sterically bulky ethylenicallyunsaturated third monomer selected independently from: a)CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), wherein R^(1A), R^(2A), andR^(3A) are selected independently from H or an alkyl group having from 1to 6 carbon atoms, inclusive, and m is an integer from 1 to 30,inclusive; b) CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B),wherein R^(1B), R^(2B), and R^(3B) are selected independently from H oran alkyl group having from 1 to 6 carbon atoms, inclusive, and n and pare integers selected independently from 1 to 15, inclusive; c)CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(r)R^(3C), wherein R^(1C),R^(2C), and R^(3C) are selected independently from H or an alkyl grouphaving from 1 to 6 carbon atoms, inclusive, and q and r are integersselected independently from 1 to 15, inclusive; or d) any combinationthereof.
 33. The method of making a bioactive anionic polymer latexaccording to claim 22, wherein the at least one sterically bulkycomponent is at least one sterically bulky ethylenically unsaturatedthird monomer selected independently from: a)CH₂═C(R^(1A))COO(CH₂CHR^(2A)O)_(m)R^(3A), wherein R^(1A), R^(2A), andR^(3A) are selected independently from H or methyl, and m is an integerfrom 1 to 10, inclusive; b)CH₂═C(R^(1B))COO(CH₂CH₂O)_(n)(CH₂CHR^(2B)O)_(p)R^(3B), wherein R^(1B),R^(2B), and R^(3B) are selected independently from H or methyl, and nand p are integers selected independently from 1 to 10, inclusive; c)CH₂═C(R^(1C))COO(CH₂CHR^(2C)O)_(q)(CH₂CH₂O)_(n)R^(3C), wherein R^(1C),R^(2C), and R^(3C) are selected independently from H or methyl, and qand r are integers selected independently from 1 to 10, inclusive; or d)any combination thereof.
 34. The method of making a bioactive anionicpolymer latex according to claim 22, wherein the at least one stericallybulky component is selected independently from: an alkoxylated monoesterof a dicarboxylic acid; an alkoxylated diester of a dicarboxylic acid; aalkyl allyl sulfosuccinate salt; a vinyl sulfonate salt; apolyoxyethylene alkylphenyl ether; a polyoxyethylene alkylphenyl etherammonium sulfate; a polymerizable surfactant; or any combinationthereof.
 35. The method of making a bioactive anionic polymer latexaccording to claim 22, wherein the at least one sterically bulkycomponent is at least one sterically bulky polymer selectedindependently from polyvinyl alcohols, polyvinyl pyrollidone,hydroxyethyl cellulose, or any combination thereof.
 36. The method ofmaking a bioactive anionic polymer latex according to claim 22, whereinthe at least one bioactive component is selected independently fromundecylenic acid; undecylenic alcohol; the reaction product ofundecylenic acid with hydroxylethyl(meth)acrylate or polyethyleneglycol(meth)acrylate; the reaction product of undecylenic alcohol with(meth)acrylic acid, maleic anhydride, or itaconic acid; or anycombination thereof.
 37. The method of making a bioactive anionicpolymer latex according to claim 22, wherein the at least one bioactivecomponent is selected independently from copper, copper salts, silver,silver salts, zinc, zinc salts, silver oxide, zinc oxide, chlorhexidine,chlorhexidine gluconate, glutaral, halazone, hexachlorophene,nitrofurazone, nitromersol, povidone-iodine, thimerosol, C₁- toC₅-parabens, hypochlorite salts, clofucarban, clorophene,poloxamer-iodine, phenolics, mafenide acetate, aminacrine hydrochloride,quaternary ammonium salts, oxychlorosene, metabromsalan, merbromin,dibromsalan, glyceryl laurate, pyrithione salts, sodium pyrithione, zincpyrithione, (dodecyl)(diethylenediamine)glycine,(dodecyl)(aminopropyl)glycine, phenol, m-cresol, n-cresol, p-cresol,o-phenyl-phenol, resorcinol, vinyl phenol, polymeric guanidines,polymyxins, bacitracin, circulin, octapeptins, lysozmye, lysostaphin,cellulytic enzymes, vancomycin, ristocetin, actinoidins, avoparcins,tyrocidin A, gramicidin S, polyoxin D, tunicamycin, neomycin,streptomycin, or any combination thereof.
 38. The method of making abioactive anionic polymer latex according to claim 22, wherein the atleast one bioactive component is selected independently fromazaconazole, biternatol, bromuconazole, cyproconazole, diniconazole,fenbuconazole, flusilazole, flutnafol, imazalil, imibenconazole,metconazole, paclobutrazol, perfuazoate, penconazole, simeconazole,triadimefon, triadimenol, uniconazole, mancozeb, maneb, metiram, zineb,fludioxonil, fluquinconazole, difenoconazole,4,5-dimethyl-N-(2-propenyl)-2-(trimethylsilyl)-3-thiophenecarboxamide(sylthiopham),hexaconazole, etaconazole, triticonazole, flutriafol, epoxiconazole,bromuconazote, tetraconazole, myclobutanil, bitertanol, pyremethanil,cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl, azoxystrobin,ZEN90160™, fenpiclonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl,orfurace, oxadixyl, carboxin, prochloraz, triflumizole, pyrifenox,acibenzolar-S-methyl, chlorothalonil, cymoxanil, dimethomorph,famoxadone, quinoxyfen, fenpropidine, spiroxamine, triazoxide,BAS50001F™, hymexazole, pencycuron, fenamidone, guazatine, benomyl,captan, carbendazim, capropamid, ethirimol, flutolanil,fosetyl-aluminum, fuberidazole, hymexanol, kasugamycin,iminoctadine-triacetate, ipconazole, iprodione, mepronil, metalaxyl-M(mefenoxam), nuarimol, oxine-copper, oxolinic acid, perfurazoate,propamocarb hydrochloride, pyroquilon, quintozene, silthiopham, MON™65500, tecnazene, thiabendazole, thifluzamide, thiophenate-methyl,thiram, tolclofos-methyl, triflumizole, or any combination thereof. 39.The method of making a bioactive anionic polymer latex according toclaim 22, wherein the bioactive anionic polymer latex comprises fromabout 0.01% to 100% by weight of the ethylenically unsaturated firstmonomer, based on the total monomer weight.
 40. The method of making abioactive anionic polymer latex according to claim 22, wherein thebioactive anionic polymer latex comprises from 0% to about 99.99% byweight of the ethylenically unsaturated second monomer, based on thetotal monomer weight.
 41. The method of making a bioactive anionicpolymer latex according to claim 22, wherein the bioactive anionicpolymer latex comprises from about 0.01% to about 40% by weightbioactive additive, based on the total monomer weight.
 42. The method ofmaking a bioactive anionic polymer latex according to claim 22, whereinthe bioactive anionic polymer latex comprises from 0% to about 25% byweight sterically bulky component, based on the total monomer weight.43. The method of making a bioactive anionic polymer latex according toclaim 22, wherein the bioactive anionic polymer latex is substantiallydevoid of anionic surfactants.
 44. A method of making a bioactiveanionic polymer latex comprising: a) providing an aqueous compositioncomprising: i) at least one ethylenically unsaturated first monomer; ii)optionally, at least one ethylenically unsaturated second monomer thatis anionic or a precursor to an anion; iii) at least one anionicsurfactant; iv) optionally, at least one sterically bulky ethylenicallyunsaturated third monomer; v) at least one free-radical initiator; andvi) optionally, at least one nonionic surfactant; b) initiating anemulsion polymerization of the composition; and c) adding at least onebioactive component to the composition during the emulsionpolymerization process.